JP2017197611A - Film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film excellent in characteristic balance of flexibility, transparency, low stickiness and impact resistance.SOLUTION: A tube has at least two layers and contains a polypropylene resin (b) and a hydrogenated block copolymer (a), where (a) contains a polymer block (C) containing a conjugated diene compound as a main component, a polymer block (B) containing a conjugated compound as a main component and a polymer block (S) containing an aromatic vinyl compound as a main component, in the molecule, (B) contains polymer blocks (B1) and (B2), and in (a), a content of (C) is 1-20 mass%, a content of (B) is 73-97 mass%, a content of (S) is 1-15 mass%, a vinyl bond amount of (C) before hydrogenation is 1-25 mol%, a vinyl bond amount of (B1) before hydrogenation is 40 mol% or more and 60 mol% or less, a vinyl bond amount of (B2) before hydrogenation is more than 60 mol% and 100 mol% or less, and a hydrogenation ratio is 80 mol% or more.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a film.

Since polypropylene resin compositions are generally excellent in chemical resistance and mechanical properties, they are widely used in packaging materials, machine parts, automobile parts and the like.
Recently, development of non-halogen-based transparent polymer materials has been progressing due to the need for environmental problems. Especially in the film field, polypropylene resins are used, and polypropylene resins are softened and transparent according to the application. There is a demand to make it.

In the following Patent Document 1, (i) polypropylene, (b) a polybutadiene block segment (A) having a 1,4 bond content of 70% or more, and a conjugated diene compound or a vinyl fragrance containing 70% by weight or more of a conjugated diene compound. A random copolymer of a group compound and a conjugated diene compound, which is a block copolymer composed of a block segment (B) in which the vinyl bond content of the conjugated diene compound portion is 60% or more, Hydrogenated diene polymer in which at least 80% of the bonds are saturated (c) Olefin polymer mainly composed of ethylene 0 to 98% by weight [However, (ii) + (b) + (c) = 100% by weight A medical flexible molded article comprising:
Moreover, in patent document 2, in the multilayer laminated body in which surface layer (II) was provided on the at least one surface of base layer (I), this base layer (I) is the following (a) / (b) = 100-20 A multilayer laminate comprising: / 0 to 80% by weight, and the surface layer (II) comprising: ((I) Polyolefin resin, (b) Hydrogenated diene copolymer having a number average molecular weight of 50,000 to 700,000, wherein the double bond of the conjugated diene moiety of the conjugated diene polymer is saturated by 80% or more (C) a hydrogenated diene copolymer having at least one terminal of a hydrogenated block of a polybutadiene polymer having a 1,2-vinyl bond-containing butadiene content of 25% or less. Yes.

JP 2000-93490 A JP-A-9-327893

The molded product of the polypropylene resin composition used in the food packaging field, the clothing packaging field, and the medical field is required to have transparency, flexibility, low stickiness, and excellent impact resistance. A good balance between these characteristics is required.
However, in the molded article as described in Patent Document 1 and the multilayer laminate disclosed in Patent Document 2, all of them are flexible, transparent, low stickiness, impact resistance, and their properties. There is still room for improvement in balance.

Therefore, in the present invention, in view of the problems of the above-described conventional technology, the hydrogenated block copolymer (a) having a specific structure is included, and flexibility, transparency, low stickiness, impact resistance, and these characteristics are included. It aims at providing the film excellent in balance.
That is, the present invention is as follows.

[1]
A film having at least two layers,
At least one layer comprises polypropylene resin (b) and hydrogenated block copolymer (a);
The hydrogenated block copolymer (a) is in the molecule,
A polymer block (C) mainly composed of a conjugated diene compound;
A polymer block (B) mainly composed of a conjugated diene compound;
A polymer block (S) mainly composed of an aromatic vinyl compound;
Including,
The polymer block (B) includes polymer blocks (B1) and (B2),
In the hydrogenated block copolymer (a), the content of the polymer block (C) is 1 to 20% by mass, the content of the polymer block (B) is 73 to 97% by mass, The content of the polymer block (S) is 1 to 15% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C) is 1 to 25 mol%, the amount of vinyl bonds before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less, The vinyl bond amount before hydrogenation of the combined block (B2) is more than 60 mol% and 100 mol% or less,
The hydrogenation rate is 80 mol% or more,
the film.
[2]
[1] The total content of the polymer block (C) and the polymer block (S) in 100% by mass of the hydrogenated block copolymer (a) is 3 to 27% by mass. Film.
[3]
In 100 mass% of the hydrogenated block copolymer (a), the content of the polymer block (B1) is 10 to 60 mass%, and the content of the polymer block (B2) is 30 to 80 mass%. %, The film according to [1] or [2].
[4]
A film having at least two layers,
At least one layer comprises polypropylene resin (b) and hydrogenated block copolymer (a);
The hydrogenated block copolymer (a) contains an aromatic vinyl compound unit and a conjugated diene compound unit in the molecule,
The content of the aromatic vinyl compound unit of the hydrogenated block copolymer (a) is 1 to 15% by mass,
The hydrogenation rate of the hydrogenated block copolymer (a) is 80 mol% or more,
The amount of butylene and / or propylene is 42 to 80 mol% with respect to a total of 100 mol% of the conjugated diene compound units in the hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) has a crystallization peak at −20 to 80 ° C. and a crystallization heat amount of 0.1 to 10 J / g, and the hydrogenated block copolymer (a) The Shore A hardness of 15-60,
The hydrogenated block copolymer (a) has an elution amount peak measured by thermal gradient interaction chromatography (TGIC) in the range of 0 ° C. or higher and 150 ° C. or lower, and the half width of the elution amount peak is 20 to 40 ° C. The range of the film.
[5]
It has at least three layers: outer layer, intermediate layer, inner layer,
The outer layer contains a polypropylene resin (b),
The intermediate layer includes a polypropylene resin (b) and the hydrogenated block copolymer (a),
The inner layer contains a polypropylene resin (b),
The film according to any one of [1] to [4].
[6]
The outer layer has a thickness of 5 to 50 μm,
The intermediate layer has a thickness of 100 to 200 μm,
The inner layer has a thickness of 5 to 50 μm.
The film according to [5].
[7]
The tan δ peak (Tg1) indicating the glass transition of the hydrogenated block copolymer, observed in the temperature-loss tangent (tan δ) curve obtained by measuring the solid viscoelasticity of the hydrogenated block copolymer (a), In the range of more than −45 ° C. and less than −30 ° C.
And difference (DELTA) Tg (Tg1-Tg2) with the tan-delta peak (Tg2) observed when 30 mass% of said hydrogenated block copolymer (a) is added to homopolypropylene is 3-12 degreeC.
The film according to any one of [1] to [6].
[8]
Ratio of integrated value of 29.4 to 30.0 ppm measured by 13C-NMR and integrated value of 9.0 to 14.0 ppm (integrated value of 29.4 to 30.0 ppm / 9.0 to 14.0 ppm) Integration value)
It is in the range of the integral value obtained by the following equation (2) from the ratio of the integral value obtained by the following equation (1),
The amount of butylene is 50 to 80 mol%,
The film according to any one of [1] to [7].
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2)
[9]
The outer layer is composed of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the hydrogenated block copolymer (b1) is other than the hydrogenated block copolymer (a). Hydrogenated block copolymer),
The hydrogenated block copolymer (b1) is
A polymer block (C-1) mainly composed of a conjugated diene compound;
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S-1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b1),
The content of the polymer block (C-1) mainly composed of the conjugated diene compound is 0 to 15% by mass,
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 75 to 97% by mass,
The content of the polymer block (S-1) mainly composed of the vinyl aromatic compound is 3 to 25% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C-1) mainly composed of the conjugated diene compound is 1 to 25 mol%,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 40 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b1) is 80 mol% or more,
The content of the polypropylene resin (b) in the outer layer is 60 to 100% by mass,
The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the outer layer is 0 to 40% by mass.
The film according to [5] to [8].
[10]
The inner layer is composed of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (where the hydrogenated block copolymer (b1) is other than the hydrogenated block copolymer (a)). Hydrogenated block copolymer),
The hydrogenated block copolymer (b1) is
A polymer block (C-1) mainly composed of a conjugated diene compound;
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S-1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b1),
The content of the polymer block (C-1) mainly composed of the conjugated diene compound is 0 to 15% by mass,
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 75 to 97% by mass,
The content of the polymer block (S-1) mainly composed of the vinyl aromatic compound is 3 to 25% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C-1) mainly composed of the conjugated diene compound is 1 to 25 mol%,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 40 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b1) is 80 mol% or more, and the content of the polypropylene resin (b) in the inner layer is 50 to 95 mass%,
The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the inner layer is 5 to 50% by mass.
The film according to any one of [5] to [9].
[11]
The polymer block (B) further includes a polymer block (B3) present at the terminal of the hydrogenated block copolymer (a),
The content of the polymer block (B3) is 1 to 10% by mass in the hydrogenated block copolymer (a).
The film according to any one of [1] to [10].
[12]
The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is 100,000 to 300,000.
The film according to any one of [1] to [11].
[13]
The film according to any one of [1] to [12], wherein the microphase-separated structure of the hydrogenated block copolymer (a) forms a spherical structure (sphere structure).
[14]
The integral elution amount measured at -20 ° C. or less measured by cross-fractionation chromatography (CFC) is 0.1% or more and less than 75% of the total volume, and the integral elution amount in the range exceeding −20 ° C. and less than 60 ° C. 5% or more and less than 80%, and the integral elution amount in the range of 60 ° C. or more and 150 ° C. or less is 20% or more and less than 95% of the total volume, the film.

  According to the present invention, it is possible to provide a film excellent in flexibility, transparency, low stickiness, impact resistance, and a balance between these properties.

The graph which shows the relationship between the amount of butylene of the hydrogenated block copolymer in this embodiment, and the ratio represented by the integral value of 29.4-30.0ppm / 9.0-14.0ppm. The transmission electron microscope (TEM) image of an example of a hydrogenation block copolymer is shown. The transmission electron microscope (TEM) image of another example of a hydrogenation block copolymer is shown.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

〔the film〕
The film of this embodiment has at least two layers.
As for the film of this embodiment, at least 1 layer contains a polypropylene resin (b) and the hydrogenated block copolymer (a) mentioned later.
By having the said structure, the film excellent in a softness | flexibility, transparency, low stickiness, impact resistance, and these property balance is obtained.

(Hydrogenated block copolymer (a))
The hydrogenated block copolymer (a) contained in the film of this embodiment comprises a polymer block (C) mainly composed of a conjugated diene compound and a polymer block (B) mainly composed of a conjugated diene compound in the molecule. And a polymer block (S) mainly composed of an aromatic vinyl compound.
The polymer block (B) mainly composed of the conjugated diene compound includes polymer blocks (B1) and (B2).
In the hydrogenated block copolymer (a), the content of the polymer block (C) mainly composed of the conjugated diene compound is 1 to 20% by mass, and the polymer block mainly composed of the conjugated diene compound ( The content of B) is 73 to 97% by mass, and the content of the polymer block (S) mainly composed of the aromatic vinyl compound is 1 to 15% by mass.
The amount of vinyl bonds before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound is 1 mol% or more and 25 mol% or less, and the amount of vinyl bonds before hydrogenation of the polymer block (B1) is 40 mol%. The amount of vinyl bonds before hydrogenation of the polymer block (B2) is more than 60 mol% and not more than 100 mol%.
The hydrogenated block copolymer (a) has a hydrogenation rate of 80 mol% or more.

Moreover, the hydrogenated block copolymer (a) mentioned above can also be specified as follows.
That is, the hydrogenated block copolymer (a) includes an aromatic vinyl compound unit and a conjugated diene compound unit in the molecule, and the content of the aromatic vinyl compound unit is 1 to 15% by mass, The hydrogenation rate of the hydrogenated block copolymer (a) is 80 mol% or more, and the amount of butylene and / or propylene is 42 to 80 mol% with respect to a total of 100 mol% of the conjugated diene compound units, and the hydrogen The block copolymer (a) has a crystallization peak at -20 to 80 ° C., the crystallization heat quantity is 0.1 to 10 J / g, and the hydrogenated block copolymer (a) has a shore A The hardness is 15-60,
The hydrogenated block copolymer (a) has an elution amount peak measured by thermal gradient interaction chromatography (hereinafter referred to as “TGIC”) in the range of 0 ° C. to 150 ° C., and the half-value width of the elution peak. Is in the range of 20-40 ° C.
Since it is comprised as mentioned above, the film of this embodiment becomes a thing excellent in a softness | flexibility, transparency, low stickiness, impact resistance, and these property balance.

The hydrogenated block copolymer (a) contained in the film of the present embodiment has a polymer block (C) mainly composed of a conjugated diene compound in the molecule (hereinafter simply referred to as “polymer block (C)”). ), A polymer block (B) mainly composed of a conjugated diene compound (hereinafter also simply referred to as “polymer block (B)”), and a polymer block mainly composed of an aromatic vinyl compound (S (Hereinafter also simply referred to as “polymer block (S)”).
Here, “mainly” means that the target monomer unit is contained in an amount of 60% by mass or more in the target polymer block.
From the viewpoint of flexibility, transparency and impact resistance of the film of the present embodiment, the content of the conjugated diene compound in the polymer block (C) and the polymer block (B) mainly composed of the conjugated diene compound is independent from each other. Then, it is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
Further, from the viewpoint of low stickiness of the hydrogenated block copolymer and the film of the present embodiment, the content of the vinyl aromatic compound in the polymer block (S) mainly composed of the vinyl aromatic compound is preferably 70 mass. % Or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
The content of the conjugated diene compound and the content of the vinyl aromatic compound can be measured by nuclear magnetic resonance spectrum analysis (NMR).
The conjugated diene compound unit is a unit constituting the hydrogenated block copolymer (a) and means a structural unit derived from the monomer of the conjugated diene compound. Moreover, an aromatic vinyl compound unit is a unit which comprises a hydrogenated block copolymer (a), Comprising: The structural unit derived from the monomer of an aromatic vinyl compound is said.

The “vinyl bond amount before hydrogenation” in the polymer blocks (C) and (B) is the bond mode of 1,2-bond, 3,4-bond and 1,4-bond of the conjugated diene before hydrogenation The ratio (mol%) of what is incorporated in 1,2-bond and 3,4-bond is incorporated.
The amount of vinyl bonds can be measured by nuclear magnetic resonance spectrum analysis (NMR).

In the film of this embodiment, the conjugated diene used for the polymer blocks (C) and (B) in the hydrogenated block copolymer (a) is a diolefin having a pair of conjugated double bonds.
Examples of the diolefin include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, Examples include 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene.
Particularly common diolefins include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.
The polymer block (C) is made of butadiene and the polymer block (B) is made of butadiene or isoprene from the viewpoints of transparency, flexibility, and impact resistance of the film of the present embodiment. preferable.

In the present embodiment, the aromatic vinyl compound used in the polymer block (S) in the hydrogenated block copolymer (a) is not limited to the following, but for example, styrene, α-methyl Examples thereof include aromatic vinyl compounds such as styrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene.
Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferably used from the viewpoints of availability and productivity. Particularly preferred is styrene.
The polymer block (S) may be composed of one type of aromatic vinyl compound unit or may be composed of two or more types.

  The content of the polymer block (C) in the hydrogenated block copolymer (a) is 1 to 20% by mass from the viewpoint of the flexibility and transparency of the film of this embodiment. From the same viewpoint, the content of the polymer block (C) in the hydrogenated block copolymer (a) is preferably 2 to 15% by mass, more preferably 3 to 10% by mass. Content of a polymer block (C) can be measured by the method described in the Example mentioned later.

The amount of vinyl bonds before hydrogenation of the polymer block (C) (hereinafter also simply referred to as “vinyl amount”) is determined from the viewpoint of dispersibility in polypropylene resin, the hydrogenated block copolymer (a) itself and the present embodiment. From the viewpoint of low stickiness of the film in the form, it is 1 mol% or more and 25 mol% or less.
From the same viewpoint, the vinyl bond amount before hydrogenation of the polymer block (C) is preferably 3 to 22 mol%, more preferably 5 to 20 mol%.
Specifically, the amount of vinyl bonds before hydrogenation of the polymer block (C) mainly composed of the conjugated diene compound can be measured by the method described in Examples described later.
The vinyl bond amount can be controlled by using a vinylating agent such as a polar compound, Lewis base, ether, amine or the like.

The content of the polymer block (B) in the hydrogenated block copolymer (a) is 73 to 97% by mass from the viewpoints of flexibility, transparency and impact resistance of the film of this embodiment.
From the same viewpoint, the content of the polymer block (B) is preferably 75 to 95% by mass, more preferably 82 to 93% by mass. Content of a polymer block (B) can be measured by the method described in the Example mentioned later.

In this embodiment, the vinyl bond amount before hydrogenation of the polymer block (B) is specified for each of the polymer block (B1) and the polymer block (B2) included in the block.
That is, the vinyl bond amount before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less from the viewpoint of impact resistance of the film of this embodiment and low stickiness of the hydrogenated block copolymer itself. is there. From the same viewpoint, the vinyl bond amount before hydrogenation of the polymer block (B1) is preferably 42 to 58 mol%, more preferably 45 to 55 mol%.
Moreover, the vinyl bond amount before hydrogenation of a polymer block (B2) is more than 60 mol% and 100 mol% or less from a viewpoint of the transparency of the film of this embodiment, and a softness | flexibility. From the same viewpoint, the amount of vinyl bonds before hydrogenation of the polymer block (B2) is preferably 65 to 95 mol%, more preferably 70 to 90 mol%.
Specifically, the amount of vinyl bonds before hydrogenation of the polymer block (B) mainly composed of the conjugated diene compound can be measured by the method described in Examples described later.
The vinyl bond amount can be controlled by using a vinylating agent such as a polar compound, Lewis base, ether, amine or the like.

As described above, the hydrogenated block copolymer (a) includes the polymer block (C) and the polymer block (B), thereby including at least three polymer blocks having different vinyl contents.
That is, a polymer block (C) that contributes to low stickiness with a low vinyl content of 1 to 25 mol%; a polymer block (B1) that contributes to impact resistance with a moderate vinyl content of 40 mol% to 60 mol% And having a polymer block (B2) that has a high vinyl content and contributes to flexibility and transparency, with more than 60 mol% and less than 100 mol%, combined with the characteristics of each polymer block, flexibility, transparency, It is particularly excellent in the balance between low stickiness and impact resistance.
That is, when the film of the present embodiment contains the hydrogenated block copolymer (a), impact resistance, low tackiness, flexibility, and transparency, which were conventionally considered to be in a trade-off relationship, The balance can be made particularly good.

In the film of the present embodiment, the polymer block (B1) in 100% by mass of the hydrogenated polymer block copolymer (a) from the viewpoint of the performance balance of flexibility, transparency, low stickiness and impact resistance. The content is preferably 10 to 60% by mass, and the content of the polymer block (B2) is preferably 30 to 80% by mass.
From the same viewpoint, the content of the polymer block (B1) is more preferably 15 to 55% by mass, and the content of the polymer block (B2) is more preferably 40 to 75% by mass. . Further, the content of the polymer block (B1) is more preferably 20 to 50% by mass, and the content of the polymer block (B2) is further preferably 50 to 70% by mass. These contents can be measured by the method described in Examples described later.

The elution amount peak measured by thermal gradient interaction chromatography (hereinafter referred to as “TGIC”) of the hydrogenated block copolymer (a) or the Soxhlet extract dry sample of the film of this embodiment is 0 ° C. or higher and 150 ° C. or lower. The half-value width of the elution amount peak is in the range of 20 to 40 ° C.
In addition, the said half value width originates in the structure of hydrogenated block copolymer (a), and when the measurement conditions are the same, when hydrogenated block copolymer (a) is used for a measurement sample, When the film containing the hydrogenated block copolymer (a) (regardless of molding conditions) is used as a measurement sample, the half width of the elution amount peak does not change.
By having the said structure, the film excellent in the balance of a softness | flexibility, transparency, low stickiness, and impact resistance is obtained.
From the same viewpoint, the half width of the elution peak in the range of 0 ° C. or higher and 150 ° C. or lower is more preferably 21 to 37 ° C., further preferably 22 to 34 ° C.
The half-width of the TGIC elution amount peak can be controlled, for example, by setting the ratio of the polymer blocks (C), (B1), and (B2) in the above range. The TGIC elution amount is described later. It can be measured by the method described in the examples.
In addition, the said half value width originates in the structure of hydrogenated block copolymer (a), and when the measurement conditions are the same, when hydrogenated block copolymer (a) is used for a measurement sample, When the film containing the hydrogenated block copolymer is used as the measurement sample, the half-value width of the elution amount peak does not change.

The content of the polymer block (S) in the hydrogenated block copolymer (a) is 1 to 15% by mass from the viewpoint of the transparency and flexibility of the film.
From the same viewpoint, the content of the polymer block (S) is preferably 2 to 12% by mass, more preferably 3 to 9% by mass.
From the same viewpoint, the content of the aromatic vinyl compound unit in the hydrogenated block copolymer (a) is 1 to 15% by mass, preferably 2 to 12% by mass, more preferably 3 -9 mass%.
The content of the polymer block (S) in the hydrogenated block copolymer and the content of the aromatic vinyl compound unit can be measured by the methods described in the examples described later.

In the hydrogenated block copolymer (a), the amount of butylene and / or propylene is 42 to 80 mol% with respect to the balance between flexibility and transparency, with respect to the total of 100 mol% of the conjugated diene compound units, Preferably it is 45-80 mol%, More preferably, it is 55-70 mol%.
The amount of butylene and / or propylene can be measured by the method described in Examples described later.
The amount of butylene and / or propylene can be controlled by the use of a vinyl compound such as a polar compound, Lewis base, ether, amine, and the hydrogenation rate.

  In the film of this embodiment, from the viewpoint of flexibility, transparency, and low stickiness, the total content of the polymer block (C) and the polymer block (S) in the hydrogenated block copolymer (a) is It is preferable that it is 3-27 mass%, More preferably, it is 5-25 mass%, More preferably, it is 7-18 mass%.

Although the structure of the hydrogenated block copolymer (a) contained in the film of this embodiment is not specifically limited, For example, what has a structure represented by a following formula is mentioned.
(CB) _n -S
(CB) _n -S- (B3)
(CBS) _n
(C-B-S) _n- (B3)
(C-B-S- (B3)) _n
(C-B-S) _m -X
(C-B-S- (B3)) _m- X
In the above formula, C, B, S, and B3 represent the polymer blocks (C), (B), (S), and (B3) described later, respectively.
When two or more are present, they may be different or the same, and one B is at least one polymer block (B1) or polymer block (B2), and a plurality of polymer blocks (B1) and polymer blocks (B2) ).
In the formula, when only one B exists, B consists of at least one polymer block (B1) and at least one polymer block (B2).
n is 1 or more, preferably an integer of 1 to 3. m shows 2 or more, Preferably it is an integer of 2-6.
X represents a coupling agent residue or a polyfunctional initiator residue.
In particular, a polymer represented by a structural formula of C—B—S or C—B—S— (B 3) is preferable.

In the film of this embodiment, from the viewpoints of flexibility and transparency, a polymer in which a polymer block polymer block (B) mainly composed of a conjugated diene is present at the terminal of the hydrogenated block copolymer (a). The block (B3) is further included, and the content of the polymer block (B3) in the hydrogenated block copolymer (a) is preferably 1 to 10% by mass.
From the same viewpoint, the content of the polymer block (B3) is more preferably 1.5 to 7% by mass and 2 to 5% by mass in the hydrogenated block copolymer (a). Further preferred.
The content of the polymer block (B3) present at the terminal of the hydrogenated block copolymer (a) can be controlled by the feed composition of the polymerization monomer.

The hydrogenation rate of the hydrogenated block copolymer (a), that is, the hydrogenation rate of all conjugated diene compound units contained in the hydrogenated block copolymer (a) is 80 mol% or more, preferably 85 mol%. It is above, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more.
The hydrogenation rate of all unsaturated group units contained in the conjugated diene monomer unit of the hydrogenated block copolymer (a) can be measured by nuclear magnetic resonance spectrum analysis (NMR), and specifically described later. It can be measured by the method described in the examples.

By setting the hydrogenation rate to 80 mol% or more, the crystallization of the polymer block (C) is enhanced, and the low stickiness of the film of this embodiment is improved.
In addition, when the resin composition obtained by mixing the hydrogenated block copolymer (a) with the polypropylene resin is used as the material of the film, the solubility parameter values of the polymer block (B) and the polypropylene resin approach, and the hydrogenation Since the dispersibility of the block copolymer (a) is improved, the flexibility and transparency of the resulting film are improved.

  The hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, and the hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, pressure and temperature.

The hydrogenated block copolymer (a) has a crystallization peak at −20 to 80 ° C. and a crystallization heat amount of 0.1 from the viewpoints of flexibility, transparency, and low stickiness of the film of the present embodiment. -10 J / g.
From the same viewpoint, the temperature range in which the crystallization peak is present is preferably −10 to 70 ° C., and more preferably 0 to 60 ° C. The crystallization heat amount is preferably 1.0 to 7.5 J / g, and more preferably 1.5 to 5.0 J / g.
The temperature range in which the crystallization peak exists and the amount of crystallization heat can be measured by the method described in the examples described later.
The crystallization peak temperature range and crystallization heat amount of the hydrogenated block copolymer (a) are determined based on the content of the polymer block (C) and the use of a vinyl compound such as a polar compound, Lewis base, ether, amine, etc. The hydrogenation rate can be controlled.

The Shore A hardness of the hydrogenated block copolymer (a) is preferably in the range of 15-60. When Shore A hardness is 15-60, the improvement effect of the softness | flexibility and impact resistance of the film of this embodiment is acquired.
The range of Shore A hardness is preferably 25 to 55, and more preferably 30 to 50.
The Shore A hardness of the hydrogenated block copolymer (a) is a polymer block mainly composed of a conjugated diene compound having a vinyl bond content of 1 to 25 mol% before hydrogenation and a polymer mainly composed of a vinyl aromatic compound. It is necessary to have a block, to adjust the content of these polymer blocks, to use a vinyl compound such as a polar compound, Lewis base, ether, amine, etc. It can be controlled by adjusting the rate.
Here, the Shore A hardness can be measured by the method described in Examples described later.

In the film of this embodiment, from the viewpoints of flexibility, transparency, and low stickiness, the microphase separation structure of the hydrogenated block copolymer (a) contained in the film includes a spherical structure (sphere structure). It is preferable.
In the hydrogenated block copolymer (a), the sphere structure is a unique structure observed when the content of the polymer block (S) is within a predetermined range or exists at one end, This can be confirmed by the method described in Examples described later.

In this embodiment, the melt flow rate (MFR; conforming to ISO 1133) of the hydrogenated block copolymer (a) is such as processability, flexibility, transparency, low stickiness, etc. of the film of this embodiment. From the viewpoint, it is preferably 0.5 to 10 g / 10 minutes, more preferably 1 to 8 g / 10 minutes or less, and further preferably 1.5 to 6 g / 10 minutes or less.
The melt flow rate is the molecular weight of the hydrogenated block copolymer (a), the content of vinyl aromatic monomer units, the amount of vinyl bonds in the conjugated diene part, the hydrogenation rate, the hydrogenated block copolymer (a) It can be controlled by adjusting the block structure or the like.
In addition, a melt flow rate can be measured by the method as described in the Example mentioned later.

In this embodiment, the hydrogenation block is observed in a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement from the viewpoint of the balance of flexibility, transparency, impact resistance and low stickiness of the film. The tan δ peak (Tg1) indicating the glass transition of the copolymer (a) is preferably in the range of more than −45 ° C. and not more than −30 ° C., and the hydrogenated block copolymer (a) Difference in tan δ peak (Tg2) ΔTg (Tg1- It is preferable that Tg2) is in the range of 3 to 12 ° C.
From the same viewpoint, it is more preferably 4 to 10 ° C, and further preferably 5 to 9 ° C.
The ΔTg can be measured by the method described in Examples described later.
The ΔTg can be controlled by the ratio of the polymer blocks (B1) and (B2) and the amount of vinyl before hydrogenation.

The weight average molecular weight (Mw) (hereinafter also referred to as “Mw”) of the hydrogenated block copolymer (a) is determined from the viewpoint of the low blocking property of the hydrogenated block copolymer (a), and the film of this embodiment. From the viewpoint of transparency, flexibility, workability, low stickiness, and balance of physical properties thereof, it is preferably 100,000 to 300,000, more preferably 130,000 to 270,000, and 150,000 to 250,000. More preferably.
Mw of the hydrogenated block copolymer (a) can be controlled by the amount of the polymerization initiator.

The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is a calibration curve obtained by measuring the molecular weight of the chromatogram peak obtained by measurement by GPC from the measurement of commercially available standard polystyrene (the peak molecular weight of standard polystyrene is The weight average molecular weight (Mw) determined based on
Specifically, it can measure by the method described in the Example mentioned later.
The total of the molecular weight distribution of the hydrogenated block copolymer, the content of the high molecular weight component, and the content of the low molecular weight component can also be determined from the measurement by GPC, and the molecular weight distribution is the weight average molecular weight (Mw) and number. This is the ratio of the average molecular weight (Mn). The total content of the high molecular weight component and the low molecular weight component, which will be described later, is obtained by dividing the total peak area of the high molecular weight component and the low molecular weight component by the total peak area. Calculated by value.

  The molecular weight distribution of a single peak measured by gel permeation chromatography (hereinafter also referred to as “GPC”) of the hydrogenated block copolymer (a) is preferably 1.30 or less, more preferably 1 .20 or less, more preferably 1.15 or less, and even more preferably 1.10 or less.

When the above-mentioned hydrogenated block copolymer (a) or the Soxhlet extract dry sample of the film of the present embodiment was measured by 13C-NMR, the integrated value of 29.4 to 30.0 ppm and 9.0 to 14.0 ppm (29.4 to 30.0 ppm integral value / 9.0 to 14.0 ppm integral value) is calculated from the ratio of the integral values obtained by the following equation (1) by the following equation (2). It is in the range of the ratio of integral values to be obtained, and the amount of butylene is preferably 50 to 80 mol%.
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2)
By setting the content in the above range, a film having excellent balance of flexibility, transparency, low stickiness, and impact resistance can be obtained.
From the same viewpoint, the amount of butylene is preferably 52 to 76 mol%, more preferably 55 to 70 mol%.
Further, in the formula representing the ratio of the integral values, it is preferably in the range of the following formula (3) to the following formula (4), more preferably in the range of the following formula (5) to the following formula (6). .
Ratio of integral values = ((1.84 + ((100-butylene content x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene content ÷ 4) (3)
Ratio of integral values = ((11.05 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (4)
Ratio of integral values = ((2.46 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (5)
Ratio of integral values = ((9.21 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (6)
The ratio of the integral values can be controlled by adjusting the amounts of the polymer blocks (C), (B1), (B2), and (S) and the amount of butylene to the above ranges.
In addition, the ratio of the integrated value is attributed to the structure of the hydrogenated block copolymer (a). If the measurement conditions are the same, the hydrogenated block copolymer (a) was used as a measurement sample. The integrated value does not change between the case and the case where the film containing the hydrogenated block copolymer (a) is used as a measurement sample.
The amount of butylene in the hydrogenated block copolymer, and the ratio of the butylene amount to the integral value calculated from the above formulas (1) to (6) (integral value of 29.4 to 30.0 ppm / 9.0 to 14) FIG. 1 shows the relationship with the integration value of .0 ppm.

[Method for Producing Hydrogenated Block Copolymer (a)]
Although it does not specifically limit as a manufacturing method of a hydrogenation block copolymer (a), For example, after polymerizing by using an organic alkali metal compound as a polymerization initiator in an organic solvent and obtaining a block copolymer, hydrogen It can manufacture by performing a chemical reaction.
The mode of polymerization may be batch polymerization, continuous polymerization, or a combination thereof. From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and high strength, a batch polymerization method is preferred.

The polymerization temperature is generally 0 to 150 ° C., preferably 20 to 120 ° C., more preferably 40 to 100 ° C., and still more preferably 55 to 65 ° C.
The polymerization time varies depending on the intended polymer, but is usually within 24 hours, preferably 0.1 to 10 hours.
From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and high strength, it is more preferably 0.5 to 3 hours.
The atmosphere of the polymerization system is not particularly limited as long as it is within a range of pressure sufficient to maintain nitrogen and the solvent in a liquid phase.
It is preferred that no impurities that inactivate the polymerization initiator and the living polymer, such as water, oxygen, carbon dioxide, etc., are present in the polymerization system.

  Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; cyclohexane and cyclohexane Alicyclic hydrocarbons such as butane and methylcyclopentane; aromatic hydrocarbons such as benzene, xylene, toluene and ethylbenzene.

As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable. As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, or an organic polylithium compound is used.
Examples of the organic lithium compound include, but are not limited to, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, phenyl lithium, hexamethylene di Examples thereof include lithium, butadienyl lithium, and isopropenyl dilithium.
Among these, n-butyllithium and sec-butyllithium are preferable from the viewpoint of polymerization activity.

  The amount of the organic alkali metal compound that is the polymerization initiator depends on the molecular weight of the target block copolymer, but is generally 0.01 to 0.5 phm (parts by mass per 100 parts by mass of the monomer). The range is preferably 0.03 to 0.3 phm, and more preferably 0.05 to 0.15 phm.

The amount of vinyl bonds in the polymer blocks (B1) and (B2) and the polymer site lock (C) contained in the hydrogenated block copolymer (a) is determined based on the presence of Lewis bases such as ethers and amines. It can be adjusted by using it as an agent.
The amount of the vinylating agent used can be adjusted according to the target vinyl bond amount.
Further, by adding a vinylating agent and a metal alkoxide described later in two or more conditions, polymer blocks having different vinyl bond amounts can be produced in a polymer block mainly composed of a conjugated diene compound. .

Examples of the vinylating agent include, but are not limited to, ether compounds, ether compounds having two or more oxygen atoms, and tertiary amine compounds.
The tertiary amine compound is not limited to the following, but for example, pyridine, N, N, N ′, N′-tetramethylethylenediamine, tributylamine, tetramethylpropanediamine, 1,2-di Examples include, but are not limited to, piperidinoethane and bis [2- (N, N-dimethylamino) ethyl] ether.
These may be used alone or in combination of two or more.
As the tertiary amine compound, a compound having two amines is preferable. Further, among them, those having a structure exhibiting symmetry within the molecule are more preferable, and N, N, N ′, N′-tetramethylethylenediamine and bis [2- (N, N-dimethylamino) ethyl] ether are preferred. And 1,2-dipiperidinoethane are more preferred.

  In the present embodiment, the hydrogenated block copolymer may be copolymerized in the presence of the above-described vinylating agent, organolithium compound, and alkali metal alkoxide. Here, the alkali metal alkoxide is a compound represented by the general formula MOR (wherein M is an alkali metal and R is an alkyl group).

The alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoints of high vinyl bond content, narrow molecular weight distribution, high polymerization rate, and high block rate.
The alkali metal alkoxide is not limited to the following, but is preferably a sodium alkoxide, a lithium alkoxide, or a potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Sodium alkoxide and potassium alkoxide having an alkyl group are preferable, and sodium-t-butoxide, sodium-t-pentoxide, potassium-t-butoxide, and potassium-t-pentoxide are more preferable.
Among these, sodium tert-butoxide and sodium tert-pentoxide are more preferable.

In the polymerization step of the hydrogenated block copolymer (a), when polymerization is carried out in the presence of a vinylating agent, an organolithium compound, and an alkali metal alkoxide, the molar ratio of the vinylating agent to the organolithium compound (vinylating agent) / Organic lithium compound) and the molar ratio of the alkali metal alkoxide to the organic lithium compound (alkali metal alkoxide / organic lithium compound) are preferably allowed to coexist in the following molar ratio.
Vinylating agent / organic lithium compound is 0.2 to 3.0.
Alkali metal alkoxide / organic lithium compound is 0.01 to 0.3

  The molar ratio of the vinylating agent / organolithium compound should be 0.2 or more from the viewpoint of a high vinyl bond amount and a high polymerization rate, and less than 3.0 from the viewpoint of obtaining a narrow molecular weight distribution and high hydrogenation activity. preferable. The molar ratio of the alkali metal alkoxide / organic lithium compound is 0.01 or more from the viewpoint of a high vinyl bond amount, a high polymerization rate, and a high block ratio, and is 0 from the viewpoint of obtaining a narrow molecular weight distribution and high hydrogenation activity. .3 or less is preferable. Thereby, the polymerization rate is improved, the vinyl bond amount of the target hydrogenated block copolymer can be increased, the molecular weight distribution can be narrowed, and the block rate tends to be improved. As a result, the performance imparted to the polypropylene resin composition, that is, low anisotropy, flexibility, transparency, smoothness, low stickiness, kink properties, and strain recovery properties tend to be better.

  In the polymerization step, the molar ratio of the vinylating agent / organolithium compound is preferably 0.8 or more from the viewpoint of a high vinyl bond amount and a high polymerization rate, and from the viewpoint of a narrow molecular weight distribution and high hydrogenation activity, 2.5. The following is preferable, and the range of 1.0 or more and 2.0 or less is more preferable.

  The molar ratio of alkali metal alkoxide / organolithium compound is preferably 0.02 or more from the viewpoint of a high vinyl bond amount, a high polymerization rate and a high block ratio, and 0.2 from the viewpoint of a narrow molecular weight distribution and high hydrogenation activity. The following are preferable, 0.03 or more and 0.1 or less are more preferable, and 0.03 or more and 0.08 or less are more preferable.

  Furthermore, the molar ratio of the alkali metal alkoxide / vinylating agent is preferably 0.010 or more from the viewpoint of a high vinyl bond amount, a high polymerization rate, and a high block ratio, realizes a narrow molecular weight distribution, and has a high hydrogen content. From the viewpoint of obtaining activating activity, it is preferably 0.100 or less, more preferably 0.012 or more and 0.080 or less, further preferably 0.015 or more and 0.06 or less, and further preferably 0.015 or more and 0.05 or less.

A deactivator for the vinylating agent can also be used as a method for producing a block having a different amount of vinyl bonds in a polymer block mainly composed of a conjugated diene compound.
Deactivators include alkyl metal compounds and are selected from alkylaluminums having 1 to 20 carbon atoms per alkyl substituent, zinc and magnesium, and mixtures thereof.

The hydrogenation method for producing the hydrogenated block copolymer (a) is not particularly limited. For example, hydrogen is supplied to the block copolymer obtained above in the presence of a hydrogenation catalyst. By hydrogenation, a hydrogenated block copolymer in which the double bond residue of the conjugated diene compound unit is hydrogenated can be obtained.
The hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, and the hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, pressure, temperature, and the like.

By pelletizing the hydrogenated block copolymer (a), pellets of the hydrogenated block copolymer (a) can be produced.
As a method of pelletization, for example, a method in which a hydrogenated block copolymer is extruded in a strand form from a single-screw or twin-screw extruder and cut in water with a rotary blade installed on the front surface of the die part; A method in which the hydrogenated block copolymer is extruded into a strand form from an extruder, water-cooled or air-cooled, and then cut by a strand cutter; For example, a method of cutting a sheet into a strip shape and then cutting the sheet into cubic pellets using a pelletizer may be used.
In addition, the magnitude | size and shape of the pellet molded object of a hydrogenation block copolymer (a) are not specifically limited.

If necessary, the hydrogenated block copolymer (a) can be blended with a pellet blocking inhibitor for the purpose of preventing pellet blocking.
Examples of the pellet blocking inhibitor include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica.
From the viewpoint of the transparency of the film of this embodiment, calcium stearate, polyethylene, and polypropylene are preferred.
A preferable amount is 500 to 6000 ppm with respect to the hydrogenated block copolymer (a). A more preferable amount is 1000 to 5000 ppm with respect to the hydrogenated block copolymer (a). The pellet blocking inhibitor is preferably blended in a state of adhering to the pellet surface, but may be included to some extent inside the pellet.

The film of this embodiment is a film having at least two layers, and at least one layer contains a hydrogenated block copolymer (a) and a polypropylene resin (b).
In the film of this embodiment, the content of the hydrogenated block copolymer (a) is preferably 10 to 70% by mass, and the content of the polypropylene resin (b) is preferably 30 to 90% by mass. .
By setting the content in the above range, a film having good transparency, flexibility, low stickiness, impact resistance, and a balance of these properties can be obtained.
From the above viewpoint, in the film of this embodiment, the content of the hydrogenated block copolymer (a) is more preferably 15 to 65% by mass, and further preferably 20 to 60% by mass. Moreover, content of polypropylene resin (b) becomes like this. More preferably, it is 35-85 mass%, More preferably, it is 40-80 mass%.

(Polypropylene resin (b))
Examples of the polypropylene resin (b) include random polypropylene resin, homopolypropylene resin, and block polypropylene resin.
The polypropylene resin (b) is preferably a random polypropylene resin from the viewpoints of flexibility and transparency.

  Here, “random” in random polypropylene is a copolymer of monomers other than propylene and propylene, and monomers other than propylene are randomly incorporated into the propylene chain and monomers other than propylene are not substantially chained. Say.

The random polypropylene is not particularly limited as long as the propylene unit content is less than 99.5% by mass. Preferable examples of the random polypropylene include a random copolymer of propylene and ethylene, or a random copolymer of propylene and an α-olefin having 4 to 20 carbon atoms.
When a random copolymer of propylene and ethylene or a random copolymer of propylene and an α-olefin having 4 to 20 carbon atoms is used as the random polypropylene, flexibility, transparency and impact resistance tend to be better. .

Examples of the α-olefin include, but are not limited to, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1- Examples include pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. Preferred are α-olefins having 2 to 8 carbon atoms, and specific examples include ethylene, 1-butene, 3-methyl-1-butene, 1-hexene and 4-methyl-1-pentene.
These α-olefins may be used alone or in combination of two or more. Moreover, random polypropylene may also be used individually by 1 type, and may be used in combination of 2 or more type.

  Among random polypropylenes, from the viewpoint of flexibility, transparency, and mechanical strength of the film of the present embodiment, propylene-ethylene random copolymer, propylene-1-butene random copolymer, and propylene-ethylene-1-butene-3. It is more preferable to use at least one selected from the group consisting of an original random copolymer.

From the viewpoints of flexibility, transparency, and balance between these properties, random polypropylene is a random copolymer of propylene and ethylene or a random copolymer of propylene and an α-olefin having 4 to 12 carbon atoms. The ethylene or α-olefin unit content is preferably more than 0.5% by mass and less than 40% by mass, and the propylene unit content is preferably 60% by mass or more and less than 99.5% by mass.
From the same viewpoint, the content of the ethylene or α-olefin unit is more preferably more than 1% by mass and less than 30% by mass, further preferably 1.5% by mass or more and less than 25% by mass, and more preferably 2% by mass or more and less than 20% by mass. Is even more preferable.
The propylene unit content is more preferably 70% by mass or more and less than 99% by mass, still more preferably 75% by mass or more and less than 98.5% by mass, and still more preferably 80% by mass or more and less than 98% by mass.
The content of propylene units, the content of ethylene units, and the content of α-olefin units in random polypropylene can be measured by a carbon nuclear magnetic resonance (13C-NMR) method.

  The melt flow rate (MFR; 230 ° C., conforming to ISO 1133) of the random polypropylene is preferably from 1 to 30 g / 10 minutes, more preferably from 1 to 25 g / 10 minutes, from the viewpoint of processability and low stickiness of the obtained film. Preferably, 2 to 20 g / 10 min is more preferable, and 3 to 15 g / 10 min is still more preferable.

The catalyst used for producing the random polypropylene is not particularly limited. For example, a polymerization method using a stereoregular catalyst is preferable.
Examples of the stereoregular catalyst include, but are not limited to, a Ziegler catalyst and a metallocene catalyst. Among these catalysts, a metallocene catalyst is preferable from the viewpoints of transparency, flexibility, and mechanical strength of the film of the present embodiment.

From the viewpoint of transparency, flexibility, and mechanical strength of the film of the present embodiment, the molecular weight distribution (Mw / Mn) of random polypropylene is preferably 3.5 or less.
Mw / Mn is more preferably 3.0 or less, and even more preferably 2.8 or less.
The lower limit value of Mw / Mn is not particularly limited, but is preferably 1.5 or more. In particular, it is preferable that random polypropylene is polymerized by a metallocene catalyst and has a molecular weight distribution (Mw / Mn) of 1.5 or more and 3.5 or less. In addition, the molecular weight distribution of random polypropylene is calculated | required from the ratio of the weight average molecular weight (Mw) obtained by the measurement by GPC, and a number average molecular weight (Mn).

(Additive)
The film of this embodiment may be used in combination with other additives depending on the required performance.
Examples of additives include, but are not limited to, release agents such as flame retardants, stabilizers, colorants, pigments, antioxidants, antistatic agents, dispersants, flow enhancers, and metal stearates. Agents, silicone oils, mineral oil softeners, synthetic resin softeners, copper damage inhibitors, crosslinking agents, nucleating agents and the like.

(Hydrogenated block copolymer (b1))
In the film of this embodiment, the hydrogenated block copolymer (b1) (provided that the hydrogenated block copolymer (b1) is a hydrogenation other than the hydrogenated block copolymer (a) is formed in at least one layer. A block copolymer).
The hydrogenated block copolymer (b1) is
A polymer block (C-1) mainly composed of a conjugated diene compound;
A polymer block (B-1) mainly composed of a conjugated diene compound (hereinafter referred to as polymer block (B-1));
A polymer block (S-1) mainly composed of a vinyl aromatic compound (hereinafter referred to as polymer block (S-1));
including.
In the hydrogenated block copolymer (b1),
The content of the polymer block (C-1) mainly composed of the conjugated diene compound is 0 to 15% by mass,
Content of the said polymer block (B-1) is 75-97 mass%,
Content of the said polymer block (S-1) is 3-25 mass%.
The amount of vinyl bonds before hydrogenation of the polymer block (C-1) mainly composed of the conjugated diene compound is 1 to 25 mol%,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) is 40 to 100 mol%.
The hydrogenation rate of the hydrogenated block copolymer (b1) is 80 mol% or more.
In the hydrogenated block copolymer (b1), the definition of “mainly”, each material of the conjugated diene compound and the vinyl aromatic compound, the amount of vinyl bonds, and the hydrogenation rate are as described above. It can be defined similarly to the polymer (a).

(Method for producing hydrogenated block copolymer (b1))
The hydrogenated block copolymer (b1) can be produced by the same method as the hydrogenated block copolymer (a) described above.
That is, using the same monomer, the content of each polymer block, the amount of vinyl bonds, the hydrogenation rate, etc. can be controlled under the same conditions.

(Structural example of hydrogenated block copolymer (b1))
Examples of the hydrogenated block copolymer (b1) described above include those having a structure represented by the following general formula.
((C-1)-(B-1)) _n- (S-1)
((C-1)-(B-1)) _n- (S-1)-(B3)
((C-1)-(B-1)-(S-1)) _n
((C-1)-(B-1)-(S-1)) _n- (B3)
((C-1)-(B-1)-(S-1)-(B3)) _n
((C-1)-(B-1)-(S-1)) _m -X
((C-1)-(B-1)-(S-1)-(B3)) _m -X
((S-1)-(B-1)) _n- (S-1)
((S-1)-(B-1)) _n- (S-1)-(B3)
((S-1)-(B-1)-(S-1)) _n
((S-1)-(B-1)-(S-1)) _n- (B3)
((S-1)-(B-1)-(S-1)-(B3)) _n
((S-1)-(B-1)-(S-1)) _m -X
In the above formula, (C-1), (B-1), (S-1), (B3) are respectively the polymer blocks (C-1), (B-1), (S-1) and the above-mentioned (B3) similar to the hydrogenated block copolymer (a) is represented. When two or more exist, they may be different or the same. The boundary line of each block does not necessarily need to be clearly distinguished.
N is 1 or more, preferably an integer of 1 to 3.
m shows 2 or more, Preferably it is an integer of 2-6. X represents a coupling agent residue or a polyfunctional initiator residue.
In particular, (C-1)-(B-1)-(S-1), (C-1)-(B-1)-(S-1)-(B3), (S-1)-(B -1)-(S-1), (S-1)-(B-1)-(S-1)-(B3) are preferable and it is a polymer represented by the structural formula.

Here, the coupling residue means that after coupling of a coupling agent used to bond a plurality of copolymers of a conjugated diene compound monomer unit and a vinyl aromatic hydrocarbon compound monomer unit. Means residue.
Examples of the coupling agent include a bifunctional coupling agent and a polyfunctional coupling agent.
Examples of the bifunctional coupling agent include, but are not limited to, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; methyl benzoate, ethyl benzoate, phenyl benzoate, phthalates, and the like. Examples include acid esters.
Examples of the polyfunctional coupling agent having three or more functional groups include, but are not limited to, polyhydric epoxy compounds such as trihydric or higher polyalcohols, epoxidized soybean oil, and diglycidyl bisphenol A; A silicon halide compound represented by R1 _(4-n) SiX _n (wherein R1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 3 or 4), and halogenated A tin compound is mentioned.
Examples of the silicon halide compound include, but are not limited to, methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and bromides thereof.
Examples of tin halide compounds include, but are not limited to, polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used.

In the above general formula, the vinyl aromatic compound monomer units in the polymer blocks (C-1), (B-1), and (S-1) are uniformly distributed but distributed in a tapered shape. May be.
When the polymer block (C-1), (B-1), (S-1) is a copolymer block of a vinyl aromatic compound monomer unit and a conjugated diene compound monomer unit, The vinyl aromatic compound monomer unit in the copolymer block may have a plurality of uniformly distributed portions and / or a plurality of portions distributed in a tapered shape. Furthermore, a plurality of portions having different vinyl aromatic compound monomer unit content may coexist in the copolymer block portion.

(Structure of the film)
The film of this embodiment is good also as a structure which has a predetermined | prescribed intermediate | middle layer between the said outer layer and the said inner layer.
In this case, it is preferable that the outer layer contains the polypropylene resin (b), the intermediate layer contains the polypropylene resin (b) and the hydrogenated block copolymer (a), and the inner layer contains the polypropylene resin (b).
The thickness of the outer layer is preferably 5 to 50 μm, the thickness of the intermediate layer is preferably 100 to 200 μm, and the thickness of the inner layer is preferably 5 to 50 μm.
By having the said structure, the film excellent in transparency, a softness | flexibility, low stickiness, and impact resistance is obtained.
Further, the thickness of the outer layer is more preferably 10 to 40 μm, further preferably 15 to 35 μm.
The thickness of the intermediate layer is more preferably 110 to 190 μm, and further preferably 120 to 180 μm.
As for the thickness of an inner layer, 10-45 micrometers is more preferable, and 15-40 micrometers is further more preferable.

As described above, the film of the present embodiment can have at least an outer layer, an intermediate layer, and an inner layer.
When the film of this embodiment has at least three layers of an outer layer, an intermediate layer, and an inner layer, the outer layer includes a polypropylene resin (b), and the intermediate layer includes a polypropylene resin (b) and a hydrogenated block copolymer (a). It is preferable that the inner layer contains a polypropylene resin (b).
60-100 mass% is preferable, as for content of the polypropylene resin (b) in the said outer layer, 65-100 mass% is more preferable, and 70-100 mass% is further more preferable.
The outer layer may contain a hydrogenated block copolymer (a). In this case, the content of the hydrogenated block copolymer (a) in the outer layer is preferably 0 to 40% by mass, 0-35 mass% is more preferable, and 0-30 mass% is further more preferable.
30-90 mass% is preferable, as for content of the polypropylene resin (b) in the said intermediate | middle layer, 35-85 mass% is more preferable, and 40-80 mass% is further more preferable.
10-70 mass% is preferable, as for content of the hydrogenated block copolymer (a) in the said intermediate | middle layer, 15-65 mass% is more preferable, and 20-60 mass% is further more preferable.
The content of the polypropylene resin (b) in the inner layer is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and further preferably 60 to 85% by mass.
The inner layer may contain a hydrogenated block copolymer (a). In this case, the content of the hydrogenated block copolymer (a) in the inner layer is preferably 5 to 50% by mass, 10-45 mass% is more preferable, and 15-40 mass% is further more preferable.
By setting it as the said composition, a film with favorable transparency, a softness | flexibility, low stickiness, impact resistance, and these property balance is obtained.

In the film of this embodiment, the outer layer has the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the hydrogenated block copolymer (b1) is hydrogenated. A hydrogenated block copolymer other than the block copolymer (a).), And the content of the polypropylene resin (b) in the outer layer is 60 to 100% by mass. It is preferable that content of the said hydrogenated block copolymer (a) and / or hydrogenated block copolymer (b1) is 0-40 mass%.
By having the said structure, the film excellent in a softness | flexibility, transparency, impact resistance, low stickiness, and these characteristic balance is obtained.
From the above viewpoint, the content of the polypropylene resin (b) in the outer layer is more preferably 65 to 100% by mass, and further preferably 70 to 100% by mass.
Further, the content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the outer layer is more preferably 0 to 35% by mass, and 0 to 30% by mass. % Is more preferable.

In the film of this embodiment, the intermediate layer has the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the hydrogenated block copolymer (b1) is hydrogen. A hydrogenated block copolymer other than the hydrogenated block copolymer (a)), the content of the polypropylene resin (b) in the intermediate layer is 30 to 90% by mass, and the intermediate The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the layer is preferably 10 to 70% by mass.
By having the said structure, the film excellent in a softness | flexibility, transparency, impact resistance, low stickiness, and these characteristic balance is obtained.
From the above viewpoint, the content of the polypropylene resin (b) in the intermediate layer is more preferably 35 to 85% by mass, and further preferably 40 to 80% by mass. The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the intermediate layer is more preferably 15 to 65% by mass, and 20 to 60%. More preferably, it is mass%.

In the film of this embodiment, the inner layer has the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the hydrogenated block copolymer (b1) is hydrogenated. A hydrogenated block copolymer other than the block copolymer (a) may be included, and the content of the polypropylene resin (b) in the inner layer is 50 to 95% by mass, It is preferable that content of the said hydrogenated block copolymer (a) and / or hydrogenated block copolymer (b1) is 5-50 mass%.
By having the said structure, the film excellent in a softness | flexibility, transparency, impact resistance, low stickiness, and these characteristic balance is obtained.
From the above viewpoint, the content of the polypropylene resin (b) in the inner layer is more preferably 55 to 95% by mass, and further preferably 60 to 85% by mass. The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the inner layer is more preferably 10 to 45% by mass, and 15 to 40% by mass. % Is more preferable.

The integral elution amount of −20 ° C. or less measured by cross fractionation chromatography (hereinafter referred to as “CFC”) of the film of this embodiment is 0.1% or more and less than 75% of the total volume, and exceeds −20 ° C. The integrated elution amount in the range of less than 60 ° C is preferably 5% or more and less than 80% of the total volume, and the integrated elution amount in the range of 60 ° C or more and 150 ° C or less is preferably 20% or more and less than 95% of the total volume.
By having the said structure, the film excellent in the softness | flexibility, transparency, low stickiness, impact resistance, and these property balance is obtained.
From the same viewpoint, the integrated elution amount at −20 ° C. or less is more preferably 2% or more and less than 70%, and further preferably 3% or more and less than 65% of the total volume.
Moreover, it is more preferable that the integrated elution amount in the range exceeding −20 ° C. and less than 60 ° C. is 10% or more and less than 75%, more preferably 15% or more and less than 70%.
Further, the integrated elution amount in the range of 60 ° C. or more and 150 ° C. or less is more preferably 25% or more and less than 90%, and further preferably 30% or more and less than 85%.
The CFC elution amount is, for example, the ratio of the polymer block (C), (B1), (B2), the blending ratio of the hydrogenated block copolymer (a), and the type of the polypropylene resin (b). The amount of CFC elution can be measured by the method described in Examples described later.

(Manufacturing method of material constituting each layer of film)
The resin material constituting each layer of the film of this embodiment is, for example, a hydrogenated block copolymer (a), a polypropylene resin (b), a hydrogenated block copolymer (b1), and others added as necessary. These components can be selected as appropriate, and can be produced by a method of dry blending them, a method of adjusting with an apparatus used for mixing ordinary polymer materials, or the like.

Although it does not specifically limit as a mixing apparatus, For example, kneading apparatuses, such as a Banbury mixer, a kneader, a lab plast mill, a single screw extruder, a twin screw extruder, are mentioned, and it manufactures by the melt mixing method using an extruder. Is preferable from the viewpoint of productivity and good kneading properties.
Although the melting temperature at the time of kneading | mixing can be set suitably, it is in the range of 130-300 degreeC normally, and it is preferable that it is the range of 150-250 degreeC.

(Film forming method)
Although the manufacturing method of the film of this embodiment is not specifically limited, For example, a T-die method, an inflation method, etc. are employable as a molding method which throws a resin composition into an extruder and extrudes.
As the inflation molding, normal air-cooled inflation molding, air-cooled two-stage inflation molding, high-speed inflation molding, water-cooled inflation molding, or the like can be adopted.
Further, a blow molding method such as direct blow or injection blow, or a press molding method may be employed.
As the extruder to be used, a single-screw or multi-screw extruder can be used, and a multilayer film obtained by multilayer extrusion using a plurality of extruders can be formed.
Moreover, it can also shape | mold directly as a film from the extruder at the time of manufacturing a resin composition.

The film of this embodiment is excellent in transparency, flexibility, low stickiness, impact resistance, and balance of these properties, as shown in the examples described later.
Taking advantage of the above characteristics, the film of this embodiment is used for packaging of various clothing, packaging of various foods, packaging of daily goods, industrial material packaging, various rubber products, laminates of resin products, leather products, paper diapers, etc. Industrial products such as stretchable tapes and dicing films, protective films used to protect building materials and steel sheets, adhesive film base materials, fresh fish trays, fruit and vegetables packs, frozen food containers and other sheet supplies, televisions, stereos, vacuum cleaners Applications for household appliances such as, bumper parts, body panels, automotive interior and exterior parts applications such as side seals, road pavement materials, waterproofing, waterproof sheets, civil engineering packing, daily necessities, leisure goods, toys, industrial goods, furniture goods, writing tools It can be used as a stationery such as a transparent pocket, a holder, a file back cover, and a medical device such as an infusion bag.
In particular, it can be suitably used as medical films and packaging materials such as food packaging materials and clothing packaging materials.

Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples.
In Examples and Comparative Examples, hydrogenated block copolymers were prepared by the method described below, films were produced, and physical properties were compared.
At that time, the characteristics of the hydrogenated block copolymer and the physical properties of the film were measured as follows.

[Method for evaluating hydrogenated block copolymer]
((1) Content of each polymer block constituting the hydrogenated block copolymer)
About 20 mL of the polymer solution sampled at each step of the polymerization process of the block copolymer before hydrogenation is injected into a 100 mL bottle sealed with 0.50 mL of n-propylbenzene and about 20 mL of toluene as an internal standard. A sample was prepared.
This sample was measured by gas chromatography equipped with a backed column carrying Apiezon grease (manufactured by Shimadzu Corporation: GC-14B). From the calibration curve of butadiene monomer and styrene monomer obtained in advance, The amount of residual monomers was determined, it was confirmed that the polymerization rate of butadiene monomer and styrene monomer was 100%, and the content of each polymer block was calculated from the following formula.
The polymerization rate of butadiene was measured under the condition of 90 ° C., and the polymerization rate of styrene was measured under the condition of 90 ° C. (10 minutes hold) to 150 ° C. temperature increase (10 ° C./min).
Content of each polymer block = (total amount of monomers fed in each step) / (total amount of monomers) × 100% by mass

((2) Vinyl bond amount before hydrogenation of each polymer block constituting the hydrogenated block copolymer)
The polymer sampled at each step of the polymerization process of the block copolymer before hydrogenation was measured by proton nuclear magnetic resonance ( ¹ H-NMR) method.
Measuring instrument is JNM-LA400 (manufactured by JEOL), deuterated chloroform is used as solvent, sample concentration is 50mg / mL, observation frequency is 400MHz, tetramethylsilane is used as chemical shift standard, pulse delay 2.904sec, scan The number of times was 64, the pulse width was 45 °, and the measurement temperature was 26 ° C.
The amount of vinyl bonds is calculated by calculating the integral value per 1H of each bond mode from the integral values of signals attributed to 1,4-bond and 1,2-bond, and then 1,4-bond and 1,2-bond. And calculated from the ratio.
Moreover, the vinyl bond amount of each polymer block was calculated by calculating the vinyl bond amount for each polymer sampled at each step of the polymerization process of the block copolymer before hydrogenation.

((3) Hydrogenation rate of unsaturated bond based on conjugated diene compound unit of hydrogenated block copolymer)
Measurement was performed by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated block copolymer after hydrogenation.
The measurement conditions and measurement data processing method were the same as in (2) above.
For the hydrogenation rate, an integrated value of a signal derived from a residual double bond of 4.5 to 5.5 ppm and a signal derived from a hydrogenated conjugated diene was calculated, and the ratio was calculated.

((4) Content of vinyl aromatic compound unit in hydrogenated block copolymer (hereinafter also referred to as “styrene content”))
Measurement was performed by proton nuclear magnetic resonance ( ¹ H-NMR) method using the polymer after hydrogenation.
Measuring instrument is JNM-LA400 (manufactured by JEOL), deuterated chloroform is used as solvent, sample concentration is 50mg / mL, observation frequency is 400MHz, tetramethylsilane is used as chemical shift standard, pulse delay 2.904sec, scan The number of times was 64, the pulse width was 45 °, and the measurement temperature was 26 ° C.
The styrene content was calculated using the integrated value of the total styrene aromatic signal at 6.2-7.5 ppm of the spectrum.
Further, the content of the total vinyl aromatic compound was calculated by calculating the content of the vinyl aromatic compound unit for each polymer sampled at each step of the polymerization process of the block copolymer before hydrogenation.

((5) Amount of butylene and / or propylene with respect to a total of 100 mol% of conjugated diene compound units)
Measurement was performed by proton nuclear magnetic resonance ( ¹ H-NMR) using the hydrogenated block copolymer after hydrogenation.
The measurement conditions and the measurement data processing method were the same as in (2) and (3) above.
The butylene content was calculated from the ratio of the integral value of the signal attributed to butylene (hydrogenated 1,2-bond) at 0 to 2.0 ppm of the spectrum.

((6) DSC measurement)
Each 10 mg of hydrogenated block copolymer is precisely weighed in an aluminum pan, and a nitrogen atmosphere (flow rate is 50 mL / min) using a differential scanning calorimeter (DSC) (manufactured by TA Instruments Inc., Q2000). ), The temperature was raised to 150 ° C. at an initial temperature of −50 ° C. and a heating rate of 10 ° C./min, held at 150 ° C. for 5 minutes, and then cooled to −50 ° C. at 10 ° C./min.
The crystallization peak that appears in the temperature-decreasing process of the drawn DSC curve was defined as the crystallization temperature (° C.), and the amount of heat indicated by the crystallization peak area was defined as the crystallization heat amount (J / g).

((7) Temperature-loss tangent (tan δ) measurement obtained by solid viscoelasticity (1 Hz) of hydrogenated block copolymer)
A temperature-loss tangent (tan δ) spectrum obtained by solid viscoelasticity (1 Hz) was measured by the following method to obtain a peak temperature, maximum value, and minimum value of tan δ.
A measurement sample is set in the twist type geometry of the device ARES (trade name, manufactured by TA Instruments Inc.), the effective measurement length is 25 mm, the strain is 0.5%, the frequency is 1 Hz, and the measurement range is − The following materials were measured from 100 ° C. to 100 ° C. under conditions of a temperature rising rate of 3 ° C./min.
Sample 1: A hydrogenated block copolymer (a) was pressed into a sheet having a thickness of 2 mm at 200 ° C. for 5 minutes, then cut into a size of 10 mm in width and 35 mm in length, and used as a measurement sample. Tg1) was determined.
Sample 2: hydrogenated block copolymer (a) / homopolypropylene (manufactured by Sun Allomer, PL500A) = 30/70 was pressed into a sheet having a thickness of 2 mm at 200 ° C. for 5 minutes, and then 10 mm in width and length. The sample was cut to a size of 35 mm, and a tan δ peak (Tg2) on the low temperature side was obtained as a measurement sample.
The value of ΔTg (Tg1-Tg2) was determined from Sample 1 and Sample 2.

((8) Weight average molecular weight of hydrogenated block copolymer)
The weight average molecular weight of the hydrogenated block copolymer was measured by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, LC-10), column: TSKgelGMHXL (4.6 mm ID × 30 cm, 2), solvent: tetrahydrofuran (THF) Was obtained as a polystyrene-equivalent molecular weight by commercially available standard polystyrene.

((9) Melt flow rate (MFR) of hydrogenated block copolymer)
The MFR of the hydrogenated block copolymer and the propylene-based resin was measured at 230 ° C. and a load of 2.16 kg in accordance with ISO 1133.

((10) Microphase separation structure of hydrogenated block copolymer)
The hydrogenated block copolymer pellets obtained in the production example were hot-press molded at 200 ° C., and a 2 mm thick sheet was frozen with liquid nitrogen. The polymer block (S) phase was dyed with an acid, washed with water, dried, and then observed with a transmission electron microscope (TEM) at a magnification of 50,000 times.
Using image analysis software (A image-kun, manufactured by Asahi Kasei Engineering Co., Ltd.) The average value was calculated, the average particle diameter was calculated as the average value of the major axis and the minor axis, and evaluated according to the following criteria.
○: The polymer block (S) forms a microphase separation, and has a spherical structure (sphere structure) having an average particle diameter of 5 to 20 nm.
X: The polymer block (S) forms a microphase separation structure other than the above “◯”. Alternatively, a microphase separation structure is not formed.
FIG. 2 shows a TEM image when the evaluation is “◯”, and FIG. 3 shows a TEM image when the evaluation is “x”.

((11) TGIC measurement elution amount peak half-width of hydrogenated block copolymer)
The hydrogenated block copolymer after hydrogenation, and the extract obtained by Soxhlet extraction (chloroform solvent 90 ° C. × 8 hr) of the films obtained in Examples and Comparative Examples were dissolved in orthodichlorobenzene as follows. The solution sample was injected into a graphite carbon column, and the elution amount (mass%) of the sample and the temperature in the column (° C.) at that time were calculated.
The elution amount at each temperature was determined from the elution temperature-elution amount curve obtained from the value.
First, the column containing the filler is heated to 95 ° C., 0.2 mL of a sample solution in which the hydrogenated block copolymer is dissolved in orthodichlorobenzene is introduced, and the temperature of the column is lowered by 2 ° C./min. The temperature was lowered to -20 ° C. Thereafter, the column temperature was raised to 165 ° C. at a rate of temperature rise of 2 ° C./min, the mobile phase flow rate was 0.5 mL / min, and the concentration of the sample eluted at each temperature was detected. And the elution temperature-elution amount curve was measured and the elution amount in each temperature was calculated | required.
Apparatus: High-throughput composition analyzer (manufactured by Polymer Char)
Detector: IR5 type infrared spectrophotometer (manufactured by Polymer Char)
Detection wavelength: concentration sensor CH ₂ v3.42 μm (2920 cm ⁻¹ ), methyl sensor CH ₃ v 3.38 μm (2960 cm ⁻¹ )
Column: Porous graphite carbon column, Hypercarb high temperature compatible type (manufactured by Polymer Char), inner diameter 4.6 mm, length 150 mm, particle diameter 5 μm
・ Mobile phase: orthodichlorobenzene, BHT added ・ Sample concentration: 8 mg / 8 mL
Melting conditions: 150 ° C., 60 minutes (under nitrogen atmosphere)
・ Injection volume: 0.2 mL
・ Temperature drop condition: 95 ° C. to −20 ° C. (2 ° C./min), flow rate 0.0 mL / min ・ Temperature rise condition: −20 ° C. to −165 ° C. (2 ° C./min), flow rate 0.5 mL / min From the elution temperature-elution amount curve, the half width of the elution peak in the range of 0 ° C. or higher and 150 ° C. or lower was determined.

((12) Shore A hardness of hydrogenated block copolymer)
The Shore A hardness (according to ASTM D-2240) of the hydrogenated block copolymer is compression-molded with the hydrogenated block copolymer, and a sheet having a thickness of 2 mm is press-molded at 200 ° C. for 5 minutes. The sheets were stacked and the instantaneous value was measured with a durometer type A.

((13) 13C-NMR measurement and calculation of the ratio between the integrated value of 29.4 to 30.0 ppm and the integrated value of 9.0 to 14.0 ppm)
The dried sample obtained by Soxhlet extraction (chloroform solvent 90 ° C. × 8 hr) of the hydrogenated block copolymer and the films obtained in Examples and Comparative Examples was dissolved in deuterated chloroform to a concentration of 10 wt / vol%. Then, 13C-NMR of the solution sample was measured under the following conditions, and the ratio of the integrated value of 29.4 to 30.0 ppm and the integrated value of 9.0 to 14.0 ppm (the integrated value of 29.4 to 30.0 ppm). Value / integral value of 9.0 to 14.0 ppm).
・ Device: Bruker Biospin Avance 600
・ Sample tube: 5mmΦ
・ Chemical shift standard of 0ppm: TMS
-Observation nucleus: 13C
・ Observation frequency: 150.91 MHz
・ Pulse program: zigg30 (quantitative measurement method)
・ Pulse width: 30 °
・ Wait time: 10 sec
-Number of integrations: 5000 times Further, the ratio of each integrated value was calculated by the following formulas (1) and (2).
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2)

[Method for evaluating film properties]
((1) Flexibility)
Films obtained in Examples and Comparative Examples were punched with JIS No. 5 test pieces to obtain measurement samples, and the tensile velocity was 200 mm / in accordance with JIS K7127 with respect to the resin flow direction (MD direction) of the measurement samples. Measurement was performed under the condition of min.
The evaluation criteria are shown below.
◎: Tensile modulus is less than 400 MPa ○: Tensile modulus is 400 MPa or more and less than 500 MPa Δ: Tensile modulus is 500 MPa or more and less than 600 MPa ×: Tensile modulus is 600 MPa or more

(2) Transparency With respect to the films obtained in Examples and Comparative Examples, haze was measured using a haze meter (NDH-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.), and transparency was evaluated.
The evaluation criteria are shown below.
◎: Haze value is less than 12 ○: Haze value is 12 or more and less than 15 Δ: Haze value is 15 or more and less than 20 ×: Haze value is 20 or more

((3) Low stickiness)
Using the films obtained in Examples and Comparative Examples as test pieces, low stickiness was evaluated using a friction tester (KES-SE, manufactured by Kato Tech Co., Ltd.).
A 2 cm long film was cut out, attached to the sensor unit, a 10 cm film was fixed to the sample stage, and the sensor unit film and the sample stage film were placed in contact with each other.
The test conditions were a sweep speed of 1 mm / second and a load of 5 g. The obtained friction coefficient μ (dimensionless) was evaluated according to the following criteria.
◎: Friction coefficient is less than 0.9 ○: Friction coefficient is 0.9 or more and less than 1.8 △: Friction coefficient is 1.8 or more and less than 2.7 ×: Friction coefficient is 2.7 or more

((4) CFC measurement elution amount of film)
Using the films obtained in Examples and Comparative Examples as test samples, the elution temperature-elution amount curve by temperature rising elution fractionation was measured as follows, and the elution amount and elution integration amount at each temperature were determined.
First, the column containing the packing material was heated to 145 ° C., a sample solution in which the hydrogenated block copolymer was dissolved in orthodichlorobenzene was introduced, and held at 140 ° C. for 30 minutes.
Next, the temperature of the column was lowered to −20 ° C. at a temperature lowering rate of 1 ° C./min, and then held for 60 minutes to deposit the sample on the surface of the filler.
Thereafter, the column temperature was sequentially raised at 5 ° C. intervals at a rate of temperature increase of 40 ° C./min, and the concentration of the sample eluted at each temperature was detected. And the elution temperature-elution amount curve was measured from the value of the elution amount (%) of the sample and the temperature in the column (° C.) at that time, and the elution amount at each temperature was determined.
Apparatus: CFC type cross-fractionation chromatograph (manufactured by Polymer Char)
Detector: IR infrared spectrophotometer (manufactured by Polymer Char)
・ Detection wavelength: 3.42 μm
Column: Shodex HT-806M x 3 (Showa Denko)
-Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)
・ Molecular weight calibration method: Standard calibration method (polystyrene conversion)
・ Eluent: Orthodichlorobenzene ・ Flow rate: 1.0 mL / min ・ Sample concentration: 120 mg / 30 mL
・ Injection volume: 0.5 mL
From the obtained elution temperature-elution volume curve, the integrated elution volume (%) in the entire volume of −20 ° C. or lower, the integrated elution volume (%) in the total volume in the range of over −20 ° C. and lower than 60 ° C., 60 The integrated elution amount (%) in the total volume in the range of from 150 ° C. to 150 ° C. was determined and expressed as “CFC area%” in Tables 3 and 4.

((5) Impact resistance)
The film was cut into a 20 cm × 13 cm test piece, and two test pieces were superposed, and then heat sealed at 145 ° C. for 2 seconds to produce a bag.
500 mL of water was put into the bag, and the remaining one side was heat-sealed under the same conditions to produce a water-filled bag.
Further, the water-filled bag was steam sterilized, and then left in a refrigerator at 4 ° C. for 24 hours, and then the bag breaking rate was measured when 10 bags were dropped from a height of 1.8 m. It was used as an index of impact resistance.
The obtained bag breaking rate was evaluated according to the following criteria.
A: Non-breakage rate is 100%
○: Non-breakage rate is 70% or more and less than 100% △: Non-breakage rate is 50% or more and less than 70% ×: Non-breakage rate is less than 50%

[Method for producing hydrogenated block copolymer]
(Preparation of hydrogenation catalyst)
The hydrogenation catalyst used for the hydrogenation reaction of the hydrogenated block copolymer was prepared by the following method.
Add 1 L of dried and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride, and add n-hexane solution containing 200 mmol of trimethylaluminum with sufficient stirring. The reaction was allowed to proceed at room temperature for about 3 days.

(Production Example 1: Hydrogenated block copolymer (a-1))
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a tank reactor with a jacket. 1 L of cyclohexane is put in the reactor, and then n-butyllithium (hereinafter also referred to as “Bu-Li”) is 0.045 parts by mass with respect to 100 parts by mass of all monomers, and N, N as a vinylating agent. , N ′, N′-tetramethylethylenediamine (hereinafter also referred to as “TMEDA”) was added in an amount of 0.05 mol with respect to 1 mol of Bu-Li.
As a first step, a cyclohexane solution containing 10 parts by mass of butadiene (butadiene concentration of 20% by mass) was added over 10 minutes, and then further polymerized for 10 minutes. During the first step polymerization, the temperature was controlled at 65 ° C.
In the second step, TMEDA was added in an amount of 0.45 mol with respect to 1 mol of Bu-Li, a cyclohexane solution containing 34 parts by mass of butadiene (butadiene concentration of 20% by mass) was added over 30 minutes, and then polymerization was performed for another 10 minutes. . The temperature was controlled at 65 ° C. during the second step polymerization.
As a third step, TMEDA was added at 1.10 mol with respect to 1 mol of Bu-Li and sodium t-pentoxide (hereinafter also referred to as “NaOAm”) at 0.05 mol with respect to 1 mol of Bu-Li, and butadiene was added. A cyclohexane solution containing 51 parts by mass (butadiene concentration of 20% by mass) was charged over 30 minutes, and then further polymerized for 10 minutes. The temperature was controlled at 60 ° C. during the third step polymerization.
As a fourth step, a cyclohexane solution (styrene concentration 20% by mass) containing 5 parts by mass of styrene was added over 10 minutes, and then polymerization was further performed for 10 minutes. During the polymerization of the fourth step, the temperature was controlled at 65 ° C.
The polymer was sampled at every step in the polymerization process of the block copolymer.
To the obtained block copolymer, the above hydrogenation catalyst is added so that the concentration in terms of titanium is 100 ppm per 100 parts by mass of the block copolymer, and the hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. went. Then, methanol was added, and then 0.25 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.
The hydrogenated block copolymer (a-1) obtained had a hydrogenation rate of 99%, MFR of 2.5 g / 10 min, weight average molecular weight (Mw) 260,000, molecular weight distribution (Mw / Mn). 08.

(Production Example 2: Hydrogenated block copolymer (a-2))
In the second step, 32 parts by weight of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. In the third step, 48 parts by weight of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. As a step, 7 parts by mass of styrene was charged over 10 minutes and then polymerized for another 10 minutes, and as a fifth step, 3 parts by mass of butadiene was charged over 5 minutes and then polymerized for another 10 minutes ( In the same manner as in a-1), a hydrogenated block copolymer (a-2) was produced.
The obtained hydrogenated block copolymer (a-2) had a hydrogenation rate of 99%, an MFR of 3.5 g / 10 min, a weight average molecular weight (Mw) of 264,000, and a molecular weight distribution of 1.09.

(Production Example 3: Hydrogenated block copolymer (a-3))
As a first step, 15 parts by mass of butadiene is charged over 10 minutes and then polymerized for another 10 minutes. In a second step, 31 parts by mass of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. In the step, 47 parts by mass of butadiene was added over 30 minutes and then polymerized for another 10 minutes, and as the fourth step, 7 parts by mass of styrene was added over 10 minutes and then polymerized for another 10 minutes ( A hydrogenated block copolymer (a-3) was produced in the same manner as in a-1).
The obtained hydrogenated block copolymer (a-3) had a hydrogenation rate of 99%, MFR 2.3 g / 10 min, weight average molecular weight (Mw) 261,000, and molecular weight distribution 1.08.

(Production Example 4: Hydrogenated block copolymer (a-4))
Before the first step, Bu-Li is added in an amount of 0.071 parts by mass with respect to 100 parts by mass of all monomers, and as the first step, 3 parts by mass of butadiene is added over 10 minutes, and then further polymerized for 10 minutes. In 2 steps, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes, and in the third step, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. As a fourth step, 12 parts by mass of styrene was added over 10 minutes, and then polymerized for 10 minutes, in the same manner as in (a-1), the hydrogenated block copolymer (a-4) was prepared. Manufactured.
The obtained hydrogenated block copolymer (a-4) had a hydrogenation rate of 99%, an MFR of 2.3 g / 10 min, a weight average molecular weight (Mw) of 167,000, and a molecular weight distribution of 1.09.

(Production Example 5: Hydrogenated block copolymer (a-5))
As a first step, 5 parts by weight of butadiene is charged over 10 minutes, and then polymerized for another 10 minutes. In a second step, 13.5 parts by weight of butadiene is charged over 15 minutes, and then polymerized for another 10 minutes. (A-1) except that in the third step, TMEDA was added at 0.90 mole per 1 mole of Bu-Li, 76.5 parts by weight of butadiene was added over 45 minutes, and then polymerized for another 10 minutes. In the same manner as above, a hydrogenated block copolymer (a-5) was produced.
The obtained hydrogenated block copolymer (a-5) had a hydrogenation rate of 99%, MFR 4.3 g / 10 min, weight average molecular weight (Mw) 265,000, and molecular weight distribution 1.09.

(Production Example 6: Hydrogenated block copolymer (a-6))
Before the first step, Bu-Li is added in an amount of 0.047 parts by mass with respect to 100 parts by mass of all monomers. As the first step, 5 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. In 2 steps, TMEDA is added in an amount of 0.55 mol with respect to 1 mol of Bu-Li, and 55 parts by mass of butadiene is added over 30 minutes, followed by polymerization for 10 minutes. In the third step, TMEDA is added in 1 mol of Bu-Li. 1.00 mol of butadiene is added, and 37 parts by mass of butadiene is added over 30 minutes, and then further polymerized for 10 minutes. As a fourth step, 3 parts by mass of styrene is added over 10 minutes, and then for another 10 minutes. A hydrogenated block copolymer (a-6) was produced in the same manner as (a-1) except that the polymerization was performed.
The obtained hydrogenated block copolymer (a-6) had a hydrogenation rate of 99%, an MFR of 2.8 g / 10 minutes, a weight average molecular weight (Mw) of 250,000, and a molecular weight distribution of 1.07.

(Production Example 7: Hydrogenated block copolymer (a-7))
As a first step, 5 parts by mass of butadiene is charged over 10 minutes, and then polymerized for another 10 minutes. In the second step, 0.40 mol of TMEDA is added to 1 mol of Bu-Li, and 45 parts by mass of butadiene are added. Charged over 30 minutes, then polymerized for another 10 minutes. In the third step, except that 45 parts by weight of butadiene was charged over 30 minutes and then polymerized for another 10 minutes, the same as (a-1). A hydrogenated block copolymer (a-7) was produced.
The obtained hydrogenated block copolymer (a-7) had a hydrogenation rate of 99%, an MFR of 1.8 g / 10 min, a weight average molecular weight (Mw) of 262,000, and a molecular weight distribution of 1.07.

(Production Example 8: Hydrogenated block copolymer (a-8))
Without performing the first step, in the second step, 38 parts by mass of butadiene was charged over 30 minutes, and then polymerized for another 10 minutes, and in the third step, 57 parts by mass of butadiene was charged over 30 minutes, and then further A hydrogenated block copolymer (a-8) was produced in the same manner as (a-1) except that the polymerization was performed for 10 minutes.
The obtained hydrogenated block copolymer (a-8) had a hydrogenation rate of 99%, MFR 18.6 g / 10 min, weight average molecular weight (Mw) 253,000, and molecular weight distribution 1.11.

(Production Example 9: Hydrogenated block copolymer (a-9))
Before the first step, Bu4Li was added in an amount of 0.054 parts by mass with respect to 100 parts by mass of all monomers. As the first step, 25 parts by mass of butadiene was added over 10 minutes, and then polymerized for another 5 minutes. In 2 steps, 35 parts by weight of butadiene was charged over 30 minutes and then polymerized for another 10 minutes, and in the third step, 35 parts by weight of butadiene was charged over 30 minutes and then polymerized for another 10 minutes, In the same manner as (a-1), a hydrogenated block copolymer (a-9) was produced.
The obtained hydrogenated block copolymer (a-9) had a hydrogenation rate of 99%, an MFR of 1.1 g / 10 min, a weight average molecular weight (Mw) of 226,000, and a molecular weight distribution of 1.08.

(Production Example 10: Hydrogenated block copolymer (a-10))
Before the first step, Bu-Li is added in an amount of 0.105 parts by mass with respect to 100 parts by mass of all monomers. As the first step, 15 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. In 2 steps, 30 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. In 3rd step, 30 parts by mass of butadiene is charged over 30 minutes, and then polymerized for another 10 minutes. As above, a hydrogenated block copolymer (a-10) was produced in the same manner as (a-1) except that 25 parts by mass of styrene was charged over 15 minutes and then polymerized for another 10 minutes.
The obtained hydrogenated block copolymer (a-10) had a hydrogenation rate of 99%, an MFR of 3.1 g / 10 minutes, a weight average molecular weight (Mw) of 100,000, and a molecular weight distribution of 1.09.

(Production Example 11: Hydrogenated block copolymer (a-11))
Before the first step, Bu-Li is added in an amount of 0.040 parts by mass with respect to 100 parts by mass of the total monomers. As the first step, 15 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. In 2 steps, 34 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes, and in the third step, 50.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. As 4 steps, hydrogenated block copolymer (a-11) was prepared in the same manner as in (a-1) except that 0.5 part by weight of styrene was charged over 5 minutes and then further polymerized for 5 minutes. Manufactured.
The obtained hydrogenated block copolymer (a-11) had a hydrogenation rate of 99%, MFR of 25.5 g / 10 minutes, a weight average molecular weight (Mw) of 308,000 and a molecular weight distribution of 1.07.

(Production Example 12: Hydrogenated block copolymer (a-12))
Before the first step, Bu-Li is added in an amount of 0.050 part by mass with respect to 100 parts by mass of all monomers. As the first step, 5 parts by mass of butadiene is added over 10 minutes, and then polymerized for another 10 minutes. Without performing two steps, in the third step, 1.60 mol of TMEDA was added to 1 mol of Bu-Li, 90 parts by mass of butadiene was added over 60 minutes, and then polymerized for another 10 minutes. As described above, a hydrogenated block copolymer (a-12) was produced in the same manner as (a-1) except that 5 parts by mass of styrene was charged over 10 minutes and then further polymerized for 10 minutes.
The obtained hydrogenated block copolymer (a-12) had a hydrogenation rate of 99%, MFR of 3.2 g / 10 min, a weight average molecular weight (Mw) of 241,000, and a molecular weight distribution of 1.06.

(Production Example 13: Hydrogenated block copolymer (a-13))
Before the first step, Bu-Li was added in an amount of 0.064 parts by mass with respect to 100 parts by mass of all monomers, and as the first step, 17 parts by mass of butadiene was added over 10 minutes, and then polymerized for another 5 minutes. In 2 steps, TMEDA was added in an amount of 0.30 mol to 1 mol of Bu-Li, 62 parts by mass of butadiene was added over 45 minutes, and then polymerized for another 10 minutes. In the third step, TMEDA was added in 1 mol of Bu-Li. The hydrogenated block copolymer (a) was added in the same manner as (a-1) except that 1.25 mol of butadiene was added, 16 parts by mass of butadiene was added over 15 minutes, and then further polymerized for 10 minutes. -13) was produced.
The obtained hydrogenated block copolymer (a-13) had a hydrogenation rate of 99%, an MFR of 1.2 g / 10 min, a weight average molecular weight (Mw) of 189,000, and a molecular weight distribution of 1.08.

(Production Example 14: Hydrogenated block copolymer (a-14))
In the first step, 0.35 mol of TMEDA is added to 1 mol of Bu-Li, and in the second step, 0.15 mol of TMEDA is added to 1 mol of Bu-Li, and 42.5 parts by mass of butadiene is added to 30 parts. It was charged over a period of 10 minutes, and then polymerized for another 10 minutes. In the third step, 42.5 parts by mass of butadiene was charged over 30 minutes and then polymerized for another 10 minutes. Thus, a hydrogenated block copolymer (a-14) was produced.
The obtained hydrogenated block copolymer (a-14) had a hydrogenation rate of 99%, an MFR of 11.8 g / 10 min, a weight average molecular weight (Mw) of 258,000, and a molecular weight distribution of 1.06.

(Production Example 15: Hydrogenated block copolymer (a-15))
As a first step, 15 parts by mass of butadiene is charged over 10 minutes and then polymerized for another 5 minutes. In the second step, 0.60 mol of TMEDA is added to 1 mol of Bu-Li, and 50 parts by mass of butadiene are added. Charged for 30 minutes, and then polymerized for another 10 minutes. In the third step, 0.75 mol of TMEDA was added to 1 mol of Bu-Li, and 30 parts by mass of butadiene was charged for 30 minutes, and then further 10 A hydrogenated block copolymer (a-15) was produced in the same manner as (a-1) except that the polymerization was performed for a minute.
The obtained hydrogenated block copolymer (a-15) had a hydrogenation rate of 99%, MFR of 3.2 g / 10 min, a weight average molecular weight (Mw) of 262,000, and a molecular weight distribution of 1.09.

(Production Example 16: Hydrogenated block copolymer (a-16))
Before the first step, Bu-Li is added in an amount of 0.064 parts by mass with respect to 100 parts by mass of the total monomers, and in the second step, TMEDA is added in an amount of 0.40 mol with respect to 1 mol of Bu-Li, Into the third step, 0.15 mol of TMEDA is added to 1 mol of Bu-Li and 42.5 parts by mass of butadiene are added over 30 minutes. Then, a hydrogenated block copolymer (a-16) was produced in the same manner as (a-1) except that the polymerization was further continued for 10 minutes.
The obtained hydrogenated block copolymer (a-16) had a hydrogenation rate of 99%, an MFR of 2.0 g / 10 min, a weight average molecular weight (Mw) of 184,000, and a molecular weight distribution of 1.05.

(Production Example 17: Hydrogenated block copolymer (a-17))
In the second step, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. In the third step, 42.5 parts by mass of butadiene is charged over 30 minutes and then polymerized for another 10 minutes. Then, a hydrogenated block copolymer (a-17) was produced in the same manner as (a-1) except that the subsequent hydrogenation reaction was interrupted.
The obtained hydrogenated block copolymer (a-17) had a hydrogenation rate of 60%, an MFR of 38.8 g / 10 min, a weight average molecular weight (Mw) of 265,000, and a molecular weight distribution of 1.05.

(Production Example 18: Hydrogenated block copolymer (a-18))
Prior to the first step, 0.065 parts by mass of Bu-Li is added with respect to 100 parts by mass of the total monomers, and in the first step, 8 parts by mass of styrene is added over 10 minutes, and then further polymerized for 10 minutes, In the second step, TMEDA is added in an amount of 0.55 mol with respect to 1 mol of Bu-Li, 42 parts by mass of butadiene is added over 30 minutes, and then further polymerized for 10 minutes. In the third step, TMEDA is added to Bu-Li1. 0.80 mol is added with respect to mol, and 42 parts by mass of butadiene is added over 30 minutes, and then further polymerized for 10 minutes. In the fourth step, 8 parts by mass of styrene is added over 10 minutes, and then further 10 A hydrogenated block copolymer (a-18) was produced in the same manner as (a-1) except that the polymerization was performed for a minute.
The obtained hydrogenated block copolymer (a-18) had a hydrogenation rate of 99%, MFR 4.4 g / 10 min, weight average molecular weight (Mw) 184,000, and molecular weight distribution 1.07.

  The analysis results of the hydrogenated block copolymers (a-1) to (a-18) obtained as described above are shown in Table 1 below.

[Method for producing hydrogenated block copolymer ((b1): b1-1 to b1-4)]
(Hydrogenated block copolymer (b1-1))
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a jacketed tank reactor.
First, 1 L of cyclohexane is charged, and then n-butyllithium (hereinafter referred to as Bu-Li) is 0.065 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N ′, N′-tetramethylethylenediamine ( Hereinafter, TMEDA was added to 0.05 mol of Bu-Li with respect to 1 mol, and sodium t-pentoxide (hereinafter referred to as NaOAm) was added with 0.05 mol to 1 mol of Bu-Li.
As a first step, a cyclohexane solution (concentration: 20% by mass) containing 7 parts by mass of styrene was added over 5 minutes, and then further polymerized for 5 minutes. During polymerization, the temperature was controlled at 60 ° C.
Next, as a second step, a cyclohexane solution (concentration: 20% by mass) containing 85 parts by mass of butadiene was added over 60 minutes, and then polymerization was further performed for 5 minutes. During the polymerization, the temperature was controlled at 55 ° C.
Next, as a third step, a cyclohexane solution (concentration 20% by mass) containing 8 parts by mass of styrene was added over 5 minutes, and then polymerization was further performed for 5 minutes. During polymerization, the temperature was controlled at 60 ° C.
The obtained block copolymer had a styrene content of 15% by mass, a vinyl bond content of 78% before hydrogenation of the butadiene block part, a weight average molecular weight of 178,000, and a molecular weight distribution of 1.12.
Next, 100 ppm of the hydrogenation catalyst as titanium per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C.
Thereafter, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.
The hydrogenated block copolymer (b1-1) obtained had a hydrogenation rate of 99.2% and MFR of 4.8 g / 10 min.
Table 2 shows the analysis results of the obtained hydrogenated block copolymer (b1-1).

(Hydrogenated block copolymer (b1-2))
Bu-Li is 0.095 parts by mass with respect to 100 parts by mass of all monomers, TMEDA is added at 0.65 mol per mol of Bu-Li, and NaOAm is not added. The amount of styrene in the second step was 82 parts by mass, the amount of butadiene in the second step was 82 parts by mass, the temperature during the polymerization was controlled at 67 ° C., and the block copolymer was produced. The same operation as in the union (b1-1) was performed to produce a hydrogenated block copolymer (b1-2).
The obtained hydrogenated block copolymer (b1-2) had a styrene content of 18% by mass, a vinyl bond content of the butadiene block part of 55%, a weight average molecular weight of 121,000, a molecular weight distribution of 1.
05, hydrogenation rate was 99.0%, and MFR was 4.0 g / 10 min.
Table 2 shows the analysis results of the obtained hydrogenated block copolymer (b1-2).

(Hydrogenated block copolymer (b1-3))
Bu-Li is 0.055 parts by mass with respect to 100 parts by mass of all monomers, the first step is 10 parts by mass of butadiene, the second step is 85 parts by mass of butadiene, and TMEDA is 1 mol of Bu-Li. Hydrogenation in the same manner as (a-12) except that 0.65 mol and sodium t-pentoxide (hereinafter also referred to as “NaOAm”) was not added, and the third step was 5 parts by mass of styrene. A block copolymer (b1-3) was produced. In addition, the polymer was sampled for each step in the polymerization process of the block copolymer.
The hydrogenation rate of the obtained (b1-3) hydrogenated block copolymer was 99.4%, the styrene content was 5% by mass, the MFR was 2.9 g / 10 min, and the weight average molecular weight (Mw) was 239,000. The molecular weight distribution (Mw / Mn) was 1.08.

(Hydrogenated block copolymer (b1-4))
Batch polymerization was carried out using a stirring device having an internal volume of 10 L and a jacketed tank reactor.
First, 1 L of cyclohexane is charged, and then n-butyllithium (hereinafter referred to as Bu-Li) is 0.065 parts by mass with respect to 100 parts by mass of all monomers, and N, N, N ′, N′-tetramethylethylenediamine. (Hereinafter referred to as TMEDA) was added to 1.5 mol of Bu-Li per mol, and sodium t-pentoxide (hereinafter referred to as NaOAm) was added to 0.05 mol of Bu-Li per mol. .
As a first step, a cyclohexane solution (concentration 20% by mass) containing 6.5 parts by mass of styrene was added over 5 minutes, and then polymerized for another 5 minutes. During polymerization, the temperature was controlled at 60 ° C.
Next, as a second step, a cyclohexane solution (concentration: 20% by mass) containing 82 parts by mass of butadiene was added over 60 minutes, and then polymerized for another 5 minutes. During the polymerization, the temperature was controlled at 55 ° C.
Next, as a third step, a cyclohexane solution containing 6.5 parts by mass of styrene (concentration 20% by mass) was added over 5 minutes, and then polymerized for another 5 minutes.
Next, the 4th step was added, 5 mass parts of butadiene was thrown in over 5 minutes, and it superposed | polymerized for further 5 minutes after that. During polymerization, the temperature was controlled at 60 ° C.
The obtained block copolymer had a styrene content of 13% by mass, a vinyl bond content of 77% of the butadiene block part corresponding to the polymer block (B-1), and a butadiene block part corresponding to the polymer block (B3). The vinyl bond amount was 76%, the weight average molecular weight was 174,000, and the molecular weight distribution was 1.09.
Next, 100 ppm of the above hydrogenation catalyst as titanium per 100 parts by mass of the block copolymer was added to the obtained block copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C.
Thereafter, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer.
The hydrogenated block copolymer (b1-4) obtained had a hydrogenation rate of 99.0% and MFR of 5.0 g / 10 min.
Table 2 shows the analysis results of the obtained hydrogenated block copolymer (b1-4).

〔polypropylene〕
PP-1: ethylene / propylene random copolymer Novatec MF3FQ (manufactured by Nippon Polypro Co., Ltd., MFR: 8 g / 10 min, ethylene content: 2.5 wt%)
PP-2: Random copolymer of ethylene / propylene Novatec EG6D (manufactured by Nippon Polypro, MFR: 1.9 g / 10 min, ethylene content: 1.3 wt%)

[Examples 1-7], [Comparative Examples 1-11]
<Double-layer film-shaped molded product>
Each layer shown in Table 3 is laminated in the order shown in Table 3 (Layer 1 and Layer 2) using the materials shown in the table, and a multilayer extruder (PLABOR, manufactured by Plastic Engineering Laboratory Co., Ltd.) Was used for coextrusion molding under conditions of an extrusion temperature of 230 ° C. and a die temperature of 250 ° C. to obtain a bilayer film having a thickness of 0.17 mm.

  From the results of Table 3, the two-layer film-like molded bodies obtained in Examples 1 to 7 are practically good in all of flexibility, transparency, low stickiness, and impact resistance, and have a characteristic balance. It was found to be good.

[Examples 8 to 14]
<Three-layer film-shaped molded product>
Each layer shown in Table 4 is laminated in the order shown in Table 4 (outer layer, intermediate layer, inner layer) using the materials shown in the table, and a multi-layer extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., PLABOR). ) Was coextruded under the conditions of an extrusion temperature of 230 ° C. and a die temperature of 250 ° C. to obtain a three-layer film having a thickness of 0.17 mm.

  From the results in Table 4, the three-layer film-like molded bodies obtained in Examples 8 to 14 are practically good in all of flexibility, transparency, low stickiness, and impact resistance, and have a balance of properties. It was found to be good.

  The film of this embodiment includes various clothing packaging, various food packaging, daily miscellaneous goods packaging, industrial material packaging, various rubber products, laminates of resin products, leather products, elastic tapes used for paper diapers, and dicing films. Industrial products such as, protective films used to protect building materials and steel plates, adhesive film substrates, meat and fish trays, sheet products such as fruits and vegetables, frozen food containers, household appliances such as TVs, stereos, and vacuum cleaners, Automotive interior / exterior parts applications such as bumper parts, body panels, side seals, road paving materials, waterproofing, water shielding sheets, civil engineering packing, daily necessities, leisure goods, toys, industrial goods, furniture supplies, writing tools, transparent pockets, holders, It has industrial applicability as a stationery such as a file back cover and a medical tool such as an infusion bag. In particular, it has industrial applicability as medical films and packaging materials such as food packaging materials and clothing packaging materials.

Claims (14)

A film having at least two layers,
At least one layer comprises polypropylene resin (b) and hydrogenated block copolymer (a);
The hydrogenated block copolymer (a) is in the molecule,
A polymer block (C) mainly composed of a conjugated diene compound;
A polymer block (B) mainly composed of a conjugated diene compound;
A polymer block (S) mainly composed of an aromatic vinyl compound;
Including,
The polymer block (B) includes polymer blocks (B1) and (B2),
In the hydrogenated block copolymer (a), the content of the polymer block (C) is 1 to 20% by mass, the content of the polymer block (B) is 73 to 97% by mass, The content of the polymer block (S) is 1 to 15% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C) is 1 to 25 mol%, the amount of vinyl bonds before hydrogenation of the polymer block (B1) is 40 mol% or more and 60 mol% or less, The vinyl bond amount before hydrogenation of the combined block (B2) is more than 60 mol% and 100 mol% or less,
The hydrogenation rate is 80 mol% or more,
the film.   The total content of the polymer block (C) and the polymer block (S) in 100% by mass of the hydrogenated block copolymer (a) is 3 to 27% by mass. The film described.   In 100 mass% of the hydrogenated block copolymer (a), the content of the polymer block (B1) is 10 to 60 mass%, and the content of the polymer block (B2) is 30 to 80 mass%. The film according to claim 1, wherein the film is%. A film having at least two layers,
At least one layer comprises polypropylene resin (b) and hydrogenated block copolymer (a);
The hydrogenated block copolymer (a) contains an aromatic vinyl compound unit and a conjugated diene compound unit in the molecule,
The content of the aromatic vinyl compound unit of the hydrogenated block copolymer (a) is 1 to 15% by mass,
The hydrogenation rate of the hydrogenated block copolymer (a) is 80 mol% or more,
The amount of butylene and / or propylene is 42 to 80 mol% with respect to a total of 100 mol% of the conjugated diene compound units in the hydrogenated block copolymer (a),
The hydrogenated block copolymer (a) has a crystallization peak at −20 to 80 ° C. and a crystallization heat amount of 0.1 to 10 J / g, and the hydrogenated block copolymer (a) The Shore A hardness of 15-60,
The hydrogenated block copolymer (a) has an elution amount peak measured by thermal gradient interaction chromatography (TGIC) in the range of 0 ° C. or higher and 150 ° C. or lower, and the half width of the elution amount peak is 20 to 40 ° C. The range of the film. It has at least three layers: outer layer, intermediate layer, inner layer,
The outer layer contains a polypropylene resin (b),
The intermediate layer includes a polypropylene resin (b) and the hydrogenated block copolymer (a),
The inner layer contains a polypropylene resin (b),
The film as described in any one of Claims 1 thru | or 4. The outer layer has a thickness of 5 to 50 μm,
The intermediate layer has a thickness of 100 to 200 μm,
The inner layer has a thickness of 5 to 50 μm.
The film according to claim 5. The tan δ peak (Tg1) indicating the glass transition of the hydrogenated block copolymer, observed in the temperature-loss tangent (tan δ) curve obtained by measuring the solid viscoelasticity of the hydrogenated block copolymer (a), In the range of more than −45 ° C. and less than −30 ° C.
And difference (DELTA) Tg (Tg1-Tg2) with the tan-delta peak (Tg2) observed when 30 mass% of said hydrogenated block copolymer (a) is added to homopolypropylene is 3-12 degreeC.
The film as described in any one of Claims 1 thru | or 6. Ratio of integrated value of 29.4 to 30.0 ppm measured by 13C-NMR and integrated value of 9.0 to 14.0 ppm (integrated value of 29.4 to 30.0 ppm / 9.0 to 14.0 ppm) Integration value)
It is in the range of the integral value obtained by the following equation (2) from the ratio of the integral value obtained by the following equation (1),
The amount of butylene is 50 to 80 mol%,
The film as described in any one of Claims 1 thru | or 7.
Ratio of integral values = ((1.23 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (1)
Ratio of integral values = ((12.28 + ((100-butylene amount x 0.97-0.3) ÷ 0.97) ³ ÷ 10000 x 0.97) ÷ 0.97) ÷ (butylene amount ÷ 4) (2) The outer layer is composed of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (provided that the hydrogenated block copolymer (b1) is other than the hydrogenated block copolymer (a). Hydrogenated block copolymer),
The hydrogenated block copolymer (b1) is
A polymer block (C-1) mainly composed of a conjugated diene compound;
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S-1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b1),
The content of the polymer block (C-1) mainly composed of the conjugated diene compound is 0 to 15% by mass,
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 75 to 97% by mass,
The content of the polymer block (S-1) mainly composed of the vinyl aromatic compound is 3 to 25% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C-1) mainly composed of the conjugated diene compound is 1 to 25 mol%,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 40 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b1) is 80 mol% or more,
The content of the polypropylene resin (b) in the outer layer is 60 to 100% by mass,
The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the outer layer is 0 to 40% by mass.
The film according to claim 5. The inner layer is composed of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) (where the hydrogenated block copolymer (b1) is other than the hydrogenated block copolymer (a)). Hydrogenated block copolymer),
The hydrogenated block copolymer (b1) is
A polymer block (C-1) mainly composed of a conjugated diene compound;
A polymer block (B-1) mainly composed of a conjugated diene compound;
A polymer block (S-1) mainly composed of a vinyl aromatic compound;
Including,
In the hydrogenated block copolymer (b1),
The content of the polymer block (C-1) mainly composed of the conjugated diene compound is 0 to 15% by mass,
The content of the polymer block (B-1) mainly composed of the conjugated diene compound is 75 to 97% by mass,
The content of the polymer block (S-1) mainly composed of the vinyl aromatic compound is 3 to 25% by mass,
The amount of vinyl bonds before hydrogenation of the polymer block (C-1) mainly composed of the conjugated diene compound is 1 to 25 mol%,
The amount of vinyl bonds before hydrogenation of the polymer block (B-1) mainly composed of the conjugated diene compound is 40 to 100 mol%,
The hydrogenation rate of the hydrogenated block copolymer (b1) is 80 mol% or more, and the content of the polypropylene resin (b) in the inner layer is 50 to 95 mass%,
The content of the hydrogenated block copolymer (a) and / or the hydrogenated block copolymer (b1) in the inner layer is 5 to 50% by mass.
The film as described in any one of Claims 5 thru | or 9. The polymer block (B) further includes a polymer block (B3) present at the terminal of the hydrogenated block copolymer (a),
The content of the polymer block (B3) is 1 to 10% by mass in the hydrogenated block copolymer (a).
The film as described in any one of Claims 1 thru | or 10. The weight average molecular weight (Mw) of the hydrogenated block copolymer (a) is 100,000 to 300,000.
The film according to any one of claims 1 to 11.   The film according to any one of claims 1 to 12, wherein the microphase separation structure of the hydrogenated block copolymer (a) forms a spherical structure (sphere structure).   The integral elution amount measured at -20 ° C. or less measured by cross-fractionation chromatography (CFC) is 0.1% or more and less than 75% of the total volume, and the integral elution amount in the range exceeding −20 ° C. and less than 60 ° C. is the total volume. The film according to any one of claims 1 to 13, wherein the integral elution amount in the range of 60 ° C to 150 ° C is 20% to less than 95% of the total volume.